Polymerization of olefins

ABSTRACT

Disclosed herein are processes for polymerizing ethylene, acyclic olefins, and/or selected cyclic olefins, and optionally selected olefinic esters or carboxylic acids, and other monomers. The polymerizations are catalyzed by selected transition metal compounds, and sometimes other co-catalysts. Since some of the polymerizations exhibit some characteristics of living polymerizations, block copolymers can be readily made. Many of the polymers produced are often novel, particularly in regard to their microstructure, which gives some of them unusual properties. Numerous novel catalysts are disclosed, as well as some novel processes for making them. The polymers made are useful as elastomers, molding resins, in adhesives, etc. Also described herein is the synthesis of linear α-olefins by the oligomerization of ethylene using as a catalyst system a combination a nickel compound having a selected α-diimine ligand and a selected Lewis or Bronsted acid, or by contacting selected α-diimine nickel complexes with ethylene.

[0001] This application is a continuation-in-part of pending priorapplication Serial No. 60/002,654, filed Aug. 22, 1995, is also acontinuation-in-part of pending application Serial No. 60/007,375, filedAug. 8, 1995, is also a continuation-in-part of pending application Ser.No. 08/473,590, filed Jun. 7, 1995, which is a continuation-in-part ofprior pending application Ser. No. 08/415,283, filed Apr. 3, 1995, whichis a continuation-in-part of pending prior application Ser. No.08/378,044 filed Jan. 24, 1995.

FIELD OF THE INVENTION

[0002] The invention concerns novel homo- and copolymers of ethyleneand/or one or more acyclic olefins, and/or selected cyclic olefins, andoptionally selected ester, carboxylic acid, or other functional groupcontaining olefins as comonomers; selected transition metal containingpolymerization catalysts; and processes for making such polymers,intermediates for such catalysts, and new processes for making suchcatalysts. Also disclosed herein is a process for the production oflinear alpha-olefins by contacting ethylene with a nickel compound ofthe formula [DAB]NiX₂ wherein DAB is a selected α-diimine and X ischlorine, bromine, iodine or alkyl, and a selected Lewis or Bronstedacid, or by contacting ethylene with other selected α-diimine nickelcomplexes

BACKGROUND OF THE INVENTION

[0003] Homo- and copolymers of ethylene (E) and/or one or more acyclicolefins, and/or cyclic olefins, and/or substituted olefins, andoptionally selected olefinic esters or carboxylic acids, and other typesof monomers, are useful materials, being used as plastics for packagingmaterials, molded items, films, etc., and as elastomers for moldedgoods, belts of various types, in tires, adhesives, and for other uses.It is well known in the art that the structure of these variouspolymers, and hence their properties and uses, are highly dependent onthe catalyst and specific conditions used during their synthesis. Inaddition to these factors, processes in which these types of 3polymerscan be made at reduced cost are also important. Therefore, improvedprocesses for making such (new) polymers are of interest. Also disclosedherein are uses for the novel polymers.

[0004] α-Olefins are commercial materials being particularly useful asmonomers and as chemical intermediates. For a review of α-olefins,including their uses and preparation, see B. Elvers, et al., Ed.,Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A13, VCHVerlagsgesellschaft mbH, Weinheim, 1989, p. 238-251. They are useful aschemical intermediates and they are often made by the oligomerization ofethylene using various types of catalysts. Therefore catalysts which arecapable or forming α-olefins from ethylene are constantly sought.

SUMMARY OF THE INVENTION

[0005] This invention concerns a polyolefin, which contains about 80 toabout 150 branches per 1000 methylene groups, and which contains forevery 100 branches that are methyl, about 30 to about 90 ethyl branches,about 4 to about 20 propyl branches, about 15 to about 50 butylbranches, about 3 to about 15 amyl branches, and about 30 to about 140hexyl or longer branches.

[0006] This invention also concerns a polyolefin which contains about 20to about 150 branches per 1000 methylene groups, and which contains forevery 100 branches that are methyl, about 4 to about 20 ethyl branches,about 1 to about 12 propyl branches, about 1 to about 12 butyl branches,about 1 to about 10 amyl branches, and 0 to about 20 hexyl or longerbranches.

[0007] Disclosed herein is a polymer, consisting essentially of repeatunits derived from the monomers, ethylene and a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen, hydrocarbyl or substitutedhydrocarbyl, and m is 0 or an integer from 1 to 16, and which containsabout 0.01 to about 40 mole percent of repeat units derived from saidcompound, and provided that said repeat units derived from said compoundare in branches of the formula —CH(CH₂)_(n)CO₂R¹, in about 30 to about70 mole percent of said branches n is 5 or more, in about 0 to about 20mole percent n is 4, in about 3 to 60 mole percent n is 1, 2 and 3, andin about 1 to about 60 mole percent n is 0.

[0008] This invention concerns a polymer of one or more alpha-olefins ofthe formula CH₂═CH(CH₂)_(a)H wherein a is an integer of 2 or more, whichcontains the structure (XXV)

[0009] wherein R³⁵ is an alkyl group and R³⁶ is an alkyl groupcontaining two or more carbon atoms, and provided that R³⁵ is methyl inabout 2 mole percent or more of the total amount of (XXV) in saidpolymer.

[0010] This invention also includes a polymer of one or morealpha-olefins of the formula CH₂═CH(CH₂)_(a)H wherein a is an integer of2 or more, wherein said polymer contains methyl branches and said methylbranches comprise about 25 to about 75 mole percent of the totalbranches.

[0011] This invention also concerns a polyethylene containing thestructure (XXVII) in an amount greater than can be accounted for by endgroups, and preferably at least 0.5 or more of such branches per 1000methylene groups than can be accounted for by end groups.

[0012] This invention also concerns a polypropylene containing one orboth of the structures (XXVIII) and (XXIX) and in the case of (XXIX) inamounts greater than can be accounted for by end groups. Preferably atleast 0.5 more of (XXIX) branches per 1000 methylene groups than can beaccounted for by end groups, and/or at least 0.5 more of (XXVIII) per1000 methylene groups are present in the polypropylene.

[0013] Also described herein is an ethylene homopolymer with a densityof 0.86 g/ml or less.

[0014] Described herein is a process for the polymerization of olefins,comprising, contacting a transition metal complex of a bidentate ligandselected from the group consisting of

[0015] with an olefin wherein:

[0016] said olefin is selected from the group consisting of ethylene, anolefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, norbornene, or substituted norbornene;

[0017] said transition metal is selected from the group consisting ofTi, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd;

[0018] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0019] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylenesubstituted hydrocarbylene to form a carbocyclic ring;

[0020] R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ ishydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R² takentogether form a ring;

[0021] R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring;

[0022] each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

[0023] R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl;

[0024] R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

[0025] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0026] n is 2 or 3;

[0027] R¹ is hydrogen, hydrocarbyl or substituted hydrocarbyl;

[0028] and provided that:

[0029] said transition metal also has bonded to it a ligand that may bedisplace by said olefin or add to said olefin;

[0030] when M is Pd, said bidentate ligand is (VIII), (XXXII) or(XXIII);

[0031] when M is Pd a diene is not present; and

[0032] when norbornene or substituted norbornene is used no other olefinis present.

[0033] Described herein is a process for the copolymerization of anolefin and a fluorinated olefin, comprising, contacting a transitionmetal complex of a bidentate ligand selected from the group consistingof

[0034] with an olefin, and a fluorinated olefin wherein:

[0035] said olefin is selected from the group consisting of ethylene andan olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷;

[0036] said transition metal is selected from the group consisting of Niand Pd;

[0037] said fluorinated olefin is of the formulaH₂C═CH(CH₂)_(a)R_(f)R⁴²;

[0038] a is an integer of 2 to 20; R_(f) is perfluoroalkylene optionallycontaining one or more ether groups;

[0039] R⁴² is fluorine or a functional group;

[0040] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0041] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylenesubstituted hydrocarbylene to form a carbocyclic ring;

[0042] each R¹⁷ is independently saturated hydrocarbyl;

[0043] and provided that said transition metal also has bonded to it aligand that may be displaced by said olefin or add to said olefin.

[0044] This invention also concerns a copolymer of an olefin of theformula R¹⁷CH═CHR¹⁷ and a fluorinated olefin of the formulaH₂C═CH(CH₂)_(a)R_(f)R⁴², wherein:

[0045] each R¹⁷ is independently hydrogen or saturated hydrocarbyl;

[0046] a is an integer of 2 to 20; R_(f) is perfluoroalkylene optionallycontaining one or more ether groups; and

[0047] R⁴² is fluorine or a functional group;

[0048] provided that when both of R¹⁷ are hydrogen and R⁴² is fluorine,R_(f) is —(CF₂)_(b)— wherein b is 2 to 20 or perfluoroalkylenecontaining at least one ether group.

[0049] Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C.:

[0050] a first compound W, which is a neutral Lewis acid capable ofabstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anionformed is a weakly coordinating anion; or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion;

[0051] a second compound of the formula

[0052] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, or norbornene;

[0053] wherein:

[0054] M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd them oxidation state;

y+z=m

[0055] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0056] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0057] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0058] Q is alkyl, hydride, chloride, iodide, or bromide;

[0059] S is alkyl, hydride, chloride, iodide, or bromide; and

[0060] provided that:

[0061] when norbornene or substituted norbornene is present, no othermonomer is present;

[0062] when M is Pd a diene is not present; and

[0063] except when M is Pd, when both Q and S are each independentlychloride, bromide or iodide W is capable of transferring a hydride oralkyl group to M.

[0064] This invention includes a process for the production ofpolyolefins, comprising contacting, at a temperature of about −100° C.to about +200° C., one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; with a compound of the formula

[0065] wherein:

[0066] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0067] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0068] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0069] n is 2 or 3;

[0070] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound is less than about 6;

[0071] X is a weakly coordinating anion;

[0072] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0073] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0074] M is Ni(II) or Pd(II);

[0075] each R¹⁶ is independently hydrogen or alkyl containing 1 to 10carbon atoms;

[0076] n is 1, 2, or 3;

[0077] R⁸ is hydrocarbyl; and

[0078] T² is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, hydrocarbyl substituted with keto or ester groups but notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0079] and provided that:

[0080] when M is Pd a diene is not present; and

[0081] when norbornene or substituted norbornene is used no othermonomer is present.

[0082] This invention includes a process for the production ofpolyolefins, comprising contacting, at a temperature of about −100° C.to about +200° C., one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; with a compound of the formula

[0083] wherein:

[0084] R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ ishydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁵ takentogether form a ring;

[0085] R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring;

[0086] each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

[0087] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0088] R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl;

[0089] R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

[0090] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0091] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound is less than about 6; and

[0092] X is a weakly coordinating anion; and provided that:

[0093] when M is Pd or (XVIII) is used a diene is not present; and

[0094] in (XVII) M is not Pd.

[0095] This invention includes a process for the production ofpolyolefins, comprising contacting, at a temperature of about −100° C.to about +200° C., one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, 4-vinylcyclohexene, cyclobutene, cyclopentene, substitutednorbornene, and norbornene; with a compound of the formula

[0096] wherein:

[0097] R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl;

[0098] R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

[0099] T¹is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C (═O)— or R¹⁵OC(═O)—;

[0100] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound is less than about 6;

[0101] X is a weakly coordinating anion;

[0102] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0103] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0104] M is Ni(II) or Pd(II);

[0105] T² is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, hydrocarbyl substituted with keto or ester groups but notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0106] and provided that:

[0107] when M is Pd a diene is not present; and

[0108] when norbornene or substituted norbornene is used no othermonomer is present.

[0109] Described herein is a process for the production for polyolefins,comprising contacting, at a temperature of about −100° C. to about +200°C.,

[0110] a first compound W, which is a neutral Lewis acid capable ofabstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anionformed is a weakly coordinating anion; or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion;

[0111] a second compound of the formula

[0112] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, or norbornene;

[0113] wherein:

[0114] M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, ofoxidation state m;

[0115] R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁴ and R²⁸ takentogether form a ring;

[0116] R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring;

[0117] each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

[0118] n is 2 or 3;

[0119] y and z are positive integers;

y+z=m;

[0120] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0121] Q is alkyl, hydride, chloride, iodide, or bromide;

[0122] S is alkyl, hydride, chloride, iodide, or bromide; and

[0123] provided that;

[0124] when norbornene or substituted norbornene is present, no othermonomer is present.

[0125] Disclosed herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about −100° C. to about+200° C., one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene;optionally a source of X; with a compound of the formula

[0126] wherein:

[0127] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0128] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbylenesubstituted hydrocarbylene to form a ring;

[0129] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds;

[0130] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0131] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0132] E is halogen or —OR¹⁸;

[0133] R¹⁸ is hydrocarbyl not containing olefinic or acetylenic bonds;and

[0134] X is a weakly coordinating anion;

[0135] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present.

[0136] Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C.:

[0137] a first compound W, which is a neutral Lewis acid capable ofabstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anionformed is a weakly coordinating anion; or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion;

[0138] a second compound of the formula

[0139] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene,or norbornene;

[0140] wherein:

[0141] M is Ni(II), Co(II), Fe(II), or Pd(II);

[0142] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0143] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0144] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0145] Q is alkyl, hydride, chloride, iodide, or bromide;

[0146] S is alkyl, hydride, chloride, iodide, or bromide; and

[0147] provided that;

[0148] when norbornene or substituted norbornene is present, no othermonomer is present;

[0149] when M is Pd a diene is not present; and

[0150] except when M is Pd, when both Q and S are each independentlychloride, bromide or iodide W is capable of transferring a hydride oralkyl group to M.

[0151] Included herein is a polymerization process, comprising,contacting a compound of the formula [Pd(R¹³CN)₄]X₂ or a combination ofPd[OC(O)R⁴⁰]₂ and HX; a compound of the formula

[0152] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0153] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0154] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0155] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds;

[0156] R¹³ is hydrocarbyl;

[0157] R⁴⁰ is hydrocarbyl or substituted hydrocarbyl and

[0158] X is a weakly coordinating anion;

[0159] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present.

[0160] Also described herein is a polymerization process, comprising;

[0161] contacting Ni[0], Pd[0] or Ni[I] compound containing a ligandwhich may be displaced by a ligand of the formula (VIII), (XXX), (XXXII)or (XXIII);

[0162] a second compound of the formula

[0163] an oxidizing agent;

[0164] a source of a relatively weakly coordinating anion;

[0165] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;

[0166] wherein:

[0167] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0168] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0169] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0170] R¹³ is hydrocarbyl;

[0171] R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ ishydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸ takentogether form a ring;

[0172] R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring;

[0173] each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

[0174] R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0175] R⁴⁸ and R⁴⁹ are each independently hydrogen, hydrocarbyl, orsubstituted hydrocarbyl;

[0176] R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl;

[0177] n is 2 or 3;

[0178] R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl; and

[0179] X is a weakly coordinating anion;

[0180] provided that;

[0181] when norbornene or substituted norbornene is present, no othermonomer is present;

[0182] when said Pd[0] compound is used, a diene is not present; and

[0183] when said second compound is (XXX) only an Ni[0] or Ni[I]compound is used.

[0184] Described herein is a polymerization process, comprising,contacting an Ni[0] complex containing a ligand or ligands which may bedisplaced by (VIII), oxygen, an alkyl aluminum compound, and a compoundof the formula

[0185] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0186] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0187] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; and

[0188] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0189] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present.

[0190] A polymerization process, comprising, contacting oxygen and analkyl aluminum compound, or a compound of the formula HX, and a compoundof the formula

[0191] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0192] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0193] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; and

[0194] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0195] X is a weakly coordinating anion; and

[0196] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present.

[0197] Described herein is a polymerization process, comprising,contacting an Ni[0] complex containing a ligand or ligands which may bedisplaced by (VIII), HX or a Bronsted acidic solid, and a compound ofthe formula

[0198] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0199] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0200] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0201] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; and

[0202] X is a weakly coordinating anion;

[0203] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present

[0204] Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C.:

[0205] a first compound W, which is a neutral Lewis acid capable ofabstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anionformed is a weakly coordinating anion; or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion;

[0206] a second compound of the formula

[0207] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, or norbornene;

[0208] wherein:

[0209] M is Ni(II) or Pd(II);

[0210] R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl;

[0211] R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

[0212] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0213] Q is alkyl, hydride, chloride, iodide, or bromide;

[0214] S is alkyl, hydride, chloride, iodide, or bromide; and

[0215] provided that;

[0216] when norbornene or substituted norbornene is present, no othermonomer is present;

[0217] when M is Pd a diene is not present; and

[0218] except when M is Pd, when both Q and S are each independentlychloride, bromide or iodide W is capable of transferring a hydride oralkyl group to M.

[0219] This invention also concerns a process for the polymerization ofolefins, comprising, contacting, at a temperature of about −100° C. toabout +200° C., a compound of the formula

[0220] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0221] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0222] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0223] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds; and

[0224] each R²⁷ is independently hydrocarbyl;

[0225] each X is a weakly coordinating anion;

[0226] provided that, when norbornene or substituted norbornene ispresent, no other monomer is present.

[0227] This invention also concerns a process for the polymerization ofolefins, comprising, contacting, at a temperature of about −100° C. toabout +200° C.:

[0228] a first compound W, which is a neutral Lewis acid capable ofabstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anionformed is a weakly coordinating anion; or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion;

[0229] a second compound of the formula

[0230] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

[0231] R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0232] R⁴⁸ and R⁴⁹ are each independently hydrogen, hydrocarbyl, orsubstituted hydrocarbyl;

[0233] each R³¹ is independently hydrocarbyl, substituted hydrocarbyl orhydrogen;

[0234] M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe, Sc, Ni, or Pd ofoxidation state m;

[0235] y and z are positive integers;

y+z=m;

[0236] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0237] Q is alkyl, hydride, chloride, iodide, or bromide;

[0238] S is alkyl, hydride, chloride, iodide, or bromide; and

[0239] provided that;

[0240] when norbornene or substituted norbornene is present, no othermonomer is present;

[0241] when M is Pd a diene is not present; and

[0242] except when M is Pd, when both Q and S are each independentlychloride, bromide or iodide W is capable of transferring a hydride oralkyl group to M.

[0243] Disclosed herein is a compound of the formula

[0244] wherein:

[0245] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0246] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0247] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0248] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound is less than about 6;

[0249] X is a weakly coordinating anion; and

[0250] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0251] provided that when R³ and R⁴ taken together are hydrocarbylene toform a carbocyclic ring, Z is not an organic nitrile.

[0252] Described herein is a compound of the formula

[0253] wherein:

[0254] R⁵⁰ is substituted phenyl;

[0255] R⁵¹ is phenyl or substituted phenyl;

[0256] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0257] and provided that groups in the 2 and 6 positions of R⁵⁰ have adifference in E_(s) of about 0.60 or more.

[0258] Described herein is a compound of the formula

[0259] wherein:

[0260] R⁵² is substituted phenyl;

[0261] R⁵³ is phenyl or substituted phenyl;

[0262] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0263] Q is alkyl, hydride, chloride, bromide or iodide;

[0264] S is alkyl, hydride, chloride, bromide or iodide;

[0265] and provided that;

[0266] groups in the 2 and 6 positions of R⁵² have a difference in E_(s)of 0.15 or more; and

[0267] when both Q and S are each independently chloride, bromide oriodide W is capable of transferring a hydride or alkyl group to Ni.

[0268] This invention includes a compound of the formula

[0269] wherein:

[0270] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0271] R³ and R⁴ are each independently hydrogen, hydrocarbyl, orsubstituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0272] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0273] R¹⁵ is hydrocarbyl not containing an olefinic or acetylenic bond;

[0274] Z is a neutral Lewis acid wherein the donating atom is nitrogen,sulfur or oxygen, provided that, if the donating atom is nitrogen, thenthe pKa of the conjugate acid of that compound is less than about 6; and

[0275] X is a weakly coordinating anion.

[0276] This invention also concerns a compound of the formula

[0277] wherein:

[0278] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0279] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0280] M is Ni(II) or Pd(II);

[0281] each R¹⁶ is independently hydrogen or alkyl containing 1 to 10carbon atoms;

[0282] n is 1, 2, or 3;

[0283] X is a weakly coordinating anion; and

[0284] R⁸ is hydrocarbyl.

[0285] Also disclosed herein is a compound of the formula

[0286] wherein:

[0287] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0288] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0289] E is halogen or —OR¹⁸;

[0290] R¹⁸ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0291] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0292] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;and

[0293] X is a weakly coordinating anion.

[0294] Included herein is a compound of the formula[(η⁴-1,5-COD)PdT¹Z]⁺X⁻, wherein:

[0295] T¹ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0296] X is a weakly coordinating anion;

[0297] COD is 1,5-cyclooctadiene;

[0298] Z is R¹⁰CN; and

[0299] R¹⁰ is hydrocarbyl not containing olefinic or acetylenic bonds.

[0300] Also included herein is a compound of the formula

[0301] wherein:

[0302] M is Ni(II) or Pd(II);

[0303] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0304] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0305] each R¹¹ is independently hydrogen, alkyl or —(CH₂)_(m)CO₂R¹;

[0306] T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, or —CH₂CH₂CH₂CO₂R⁸;

[0307] P is a divalent group containing one or more repeat units derivedfrom the polymerization of one or more of ethylene, an olefin of theformula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene and, when M is Pd(II), optionally one or moreof: a compound of the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinylketone;

[0308] R⁸ is hydrocarbyl;

[0309] m is 0 or an integer from 1 to 16;

[0310] R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms;

[0311] and X is a weakly coordinating anion;

[0312] provided that, when M is Ni(II), R¹¹ is not —CO₂R⁸.

[0313] Also described herein is a compound of the formula

[0314] wherein:

[0315] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0316] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0317] T² is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, hydrocarbyl substituted with keto or ester groups but notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0318] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;and

[0319] X is a weakly coordinating anion.

[0320] Included herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about −100° C. to about+200° C., a compound of the formula

[0321] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,

[0322] wherein:

[0323] M is Ni(II) or Pd(II);

[0324] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0325] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0326] each R¹¹ is independently hydrogen, alkyl or —(CH₂)_(m)CO₂R¹;

[0327] T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, or —CH₂CH₂CH₂CO₂R⁸;

[0328] P is a divalent group containing one or more repeat units derivedfrom the polymerization of one or monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, and, when M is Pd(II), optionally one or more of: a compoundof the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO or a vinyl ketone;

[0329] R⁸ is hydrocarbyl;

[0330] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms;

[0331] m is 0 or an integer of 1 to 16;

[0332] and X is a weakly coordinating anion;

[0333] provided that:

[0334] when M is Pd a diene is not present;

[0335] when norbornene or substituted norbornene is present, no othermonomer is present; and

[0336] further provided that, when M is Ni(II), R¹¹ is not —CO₂R⁸.

[0337] Included herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about −100° C. to about+200° C., a compound of the formula

[0338] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,

[0339] wherein:

[0340] M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd ofoxidation state m;

[0341] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0342] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0343] each R¹¹ is independently hydrogen, or alkyl, or both of R¹¹taken together are hydrocarbylene to form a carbocyclic ring;

[0344] T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, or —CH₂CH₂CH₂CO₂R⁸;

[0345] P is a divalent group containing one or more repeat units derivedfrom the polymerization of one or monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, and, when M is Pd(II), optionally one or more of: a compoundof the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinyl ketone;

[0346] R⁸ is hydrocarbyl;

[0347] a is 1 or 2;

y+a+1=m;

[0348] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms;

[0349] m is 0 or an integer of 1 to 16;

[0350] and X is a weakly coordinating anion;

[0351] provided that:

[0352] when norbornene or substituted norbornene is present, no othermonomer is present;

[0353] when M is Pd a diene is not present; and

[0354] further provided that, when M is Ni(II), R¹¹ is not —CO₂R⁸.

[0355] Also described herein is a compound of the formula

[0356] wherein:

[0357] M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd ofoxidation state m;

[0358] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0359] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0360] each R¹¹ is independently hydrogen, or alkyl, or both of R¹¹taken together are hydrocarbylene to form a carbocyclic ring;

[0361] T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, or —CH₂CH₂CH₂CO₂R⁸;

[0362] P is a divalent group containing one or more repeat units derivedfrom the polymerization of one or monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, and optionally, when M is Pd(II), one or more of: a compoundof the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinyl ketone;

[0363] Q is a monovalent anion;

[0364] R⁸ is hydrocarbyl;

[0365] a is 1 or 2;

y+a+1=m;

[0366] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0367] R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms;

[0368] m is 0 or an integer of 1 to 16; and

[0369] and X is a weakly coordinating anion;

[0370] and provided that when M is Pd a diene is not present.

[0371] Described herein is a process, comprising, contacting, at atemperature of about −40° C. to about +60° C., a compound of the formula[(η⁴-1,5-COD)PdT¹Z]⁺X⁻ and a diimine of the formula

[0372] to produce a compound of the formula

[0373] wherein:

[0374] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R⁵OC(═O)—;

[0375] X is a weakly coordinating anion;

[0376] COD is 1,5-cyclooctadiene;

[0377] Z is R¹⁰CN;

[0378] R¹⁰ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0379] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0380] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and

[0381] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring.

[0382] Described herein is a process, comprising, contacting, at atemperature of about −80° C. to about +20° C., a compound of the formula(η⁴-1,5-COD)PdMe₂ and a diimine of the formula

[0383] to produce a compound of the formula

[0384] wherein:

[0385] COD is 1,5-cyclooctadiene;

[0386] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and

[0387] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring.

[0388] Also disclosed herein is a compound of the formula

[0389] wherein:

[0390] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0391] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0392] each R²⁷ is hydrocarbyl; and

[0393] each X is a weakly coordinating anion.

[0394] This invention includes a compound of the formula

[0395] wherein:

[0396] M is Ni(II) or Pd(II);

[0397] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0398] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0399] each R¹⁴ is independently hydrogen, alkyl or —(CH₂)_(m)CO₂R¹;

[0400] R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms;

[0401] T⁴ is alkyl, —R⁶⁰C(O)OR⁸, R¹⁵(C═O)— or R¹⁵OC(═O)—;

[0402] R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

[0403] R⁶⁰ is alkylene not containing olefinic or acetylenic bonds;

[0404] R⁸ is hydrocarbyl;;

[0405] and X is a weakly coordinating anion;

[0406] and provided that when R¹⁴ is —(CH₂)_(m)CO₂R¹, or T⁴ is notalkyl, M is Pd(II).

[0407] Described herein is a homopolypropylene with a glass transitiontemperature of −30° C. or less, and containing at least about 50branches per 1000 methylene groups.

[0408] This invention also concerns a homopolymer of cyclopentene havinga degree of polymerization of about 30 or more and an end of meltingpoint of about 100° C. to about 320° C., provided that said homopolymerhas less than 5 mole percent of enchained linear olefin containingpentylene units.

[0409] In addition, disclosed herein is a homopolymer or copolymer ofcyclopentene that has an X-ray powder diffraction pattern that hasreflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ.

[0410] Another novel polymer is a homopolymer of cyclopentene wherein atleast 90 mole percent of enchained cyclopentylene units are1,3-cyclopentylene units, and said homopolymer has an average degree ofpolymerization of 30 more.

[0411] Described herein is a homopolymer of cyclopentene wherein atleast 90 mole percent of enchained cyclopentylene units arecis-1,3-cyclopentylene, and said homopolymer has an average degree ofpolymerization of about 10 or more.

[0412] Also described is a copolymer of cyclopentene and ethylenewherein at least 75 mole percent of enchained cyclopentylene units are1,3-cyclopentylene units.

[0413] This invention concerns a copolymer of cyclopentene and ethylenewherein there are at least 20 branches per 1000 methylene carbon atoms.

[0414] Described herein is a copolymer of cyclopentene and ethylenewherein at least 50 mole percent of the repeat units are derived fromcyclopentene.

[0415] Disclosed herein is a copolymer of cyclopentene and an α-olefin.

[0416] This invention also concerns a polymerization process,comprising, contacting an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, wherein each R¹⁷ is independently hydrogen, hydrocarbyl, orsubstituted hydrocarbyl provided that any olefinic bond in said olefinis separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms with acatalyst, wherein said catalyst:

[0417] contains a nickel or palladium atom in a positive oxidationstate;

[0418] contains a neutral bidentate ligand coordinated to said nickel orpalladium atom, and wherein coordination to said nickel or palladiumatom is through two nitrogen atoms or a nitrogen atom and a phosphorousatom; and

[0419] said neutral bidentate ligand, has an Ethylene Exchange Rate ofless than 20,000 L-mol⁻¹s⁻¹ when said catalyst contains a palladiumatom, and less than 50,000 L-mol⁻¹s⁻¹ when said catalyst contains anickel atom;

[0420] and provided that when Pd is present a diene is not present.

[0421] Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C.:

[0422] a first compound which is a salt of an alkali metal cation and arelatively noncoordinating monoanion;

[0423] a second compound of the formula

[0424] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, or norbornene;

[0425] wherein:

[0426] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0427] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0428] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bond;

[0429] T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;

[0430] S is chloride, iodide, or bromide; and

[0431] provided that, when norbornene or substituted norbornene ispresent, no_other monomer is present.

[0432] Described herein is a polyolefin, comprising, a polymer made bypolymerizing one or more monomers of the formula H₂C═CH(CH₂)_(e)G bycontacting said monomers with a transition metal containing coordinationpolymerization catalyst, wherein:

[0433] each G is independently hydrogen or —CO₂R¹;

[0434] each e is independently 0 or an integer of 1 to 20;

[0435] each R¹ is independently hydrogen, hydrocarbyl or substitutedhydrocarbyl;

[0436] and provided that:

[0437] said polymer has at least 50 branches per 1000 methylene groups;

[0438] in at least 50 mole percent of said monomers G is hydrogen; and

[0439] except when no branches should be theoretically present, thenumber of branches per 1000 methylene groups is 90% or less than thenumber of theoretical branches per 1000 methylene groups, or the numberof branches per 1000 methylene groups is 110% or more of theoreticalbranches per 1000 methylene groups, and

[0440] when there should be no branches theoretically present, saidpolyolefin has 50 or more branches per 1000 methylene groups;

[0441] and provided that said polyolefin has at least two branches ofdifferent lengths containing less than 6 carbon atoms each.

[0442] Also described herein is a polyolefin, comprising, a polymer madeby polymerizing one or more monomers of the formula H₂C═CH(CH₂)_(e)G bycontacting said monomers with a transition metal containing coordinationpolymerization catalyst, wherein:

[0443] each G is independently hydrogen or —CO₂R¹;

[0444] each e is independently 0 or an integer of 1 to 20;

[0445] R¹ is independently hydrogen, hydrocarbyl or substitutedhydrocarbyl;

[0446] and provided that:

[0447] said polymer has at least 50 branches per 1000 methylene groups;

[0448] in at least 50 mole percent of said monomers G is hydrogen;

[0449] said polymer has at least 50 branches of the formula —(CH₂)_(f)Gper 1000 methylene groups, wherein when G is the same as in a monomerand e≠f, and/or for any single monomer of the formula H₂C═CH(CH₂)_(e)Gthere are less than 90% of the number of theoretical branches per 1000methylene groups, or more than 110% of the theoretical branches per 1000methylene groups of the formula —(CH₂)_(f)G and f=e, and wherein f is 0or an integer of 1 or more;

[0450] and provided that said polyolefin has at least two branches ofdifferent lengths containing less than 6 carbon atoms.

[0451] This invention concerns a process for the formation of linearα-olefins, comprising, contacting, at a temperature of about −100° C. toabout +200° C.:

[0452] ethylene;

[0453] a first compound W, which is a neutral Lewis acid capable ofabstracting X⁻ to form WX⁻, provided that the anion formed is a weaklycoordinating anion, or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion; and

[0454] a second compound of the formula

[0455] wherein:

[0456] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl;

[0457] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; and

[0458] Q and S are each independently chlorine, bromine, iodine oralkyl; and

[0459] wherein an α-olefin containing 4 to 40 carbon atoms is produced.

[0460] This invention also concerns a process for the formation oflinear α-olefins, comprising, contacting, at a temperature of about−100° C. to about +200° C.:

[0461] ethylene and a compound of the formula

[0462] wherein:

[0463] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl;

[0464] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0465] T¹ is hydrogen or n-alkyl containing up to 38 carbon atoms;

[0466] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6;

[0467] U is n-alkyl containing up to 38 carbon atoms; and

[0468] X is a noncoordinating anion;

[0469] and wherein an α-olefin containing 4 to 40 carbon atoms isproduced.

[0470] Another novel process is a process for the formation of linear(x-olefins, comprising, contacting, at a temperature of about −100° C.to about +200° C.:

[0471] ethylene;

[0472] and a Ni[II] of

[0473] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0474] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylenesubstituted hydrocarbylene to form a carbocyclic ring and

[0475] wherein an (α-olefin containing 4 to 40 carbon atoms is produced.

[0476] Also described herein is a process for the production ofpolyolefins, comprising, contacting, at a temperature of about 0° C. toabout +200° C., a compound of the formula

[0477] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,

[0478] wherein:

[0479] M is Ni(II) or Pd(II);

[0480] A is a π-allyl or π-benzyl group;

[0481] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0482] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0483] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0484] and X is a weakly coordinating anion;

[0485] and provided that:

[0486] when M is Pd a diene is not present; and

[0487] when norbornene or substituted norbornene is present, no othermonomer is present.

[0488] The invention also includes a compound of the formula

[0489] wherein:

[0490] M is Ni(II) or Pd(II);

[0491] A is a π-allyl or π-benzyl group;

[0492] R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

[0493] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0494] each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

[0495] and X is a weakly coordinating anion;

[0496] and provided that when M is Pd a diene is not present.

[0497] This invention also includes a compound of the formula

[0498] wherein:

[0499] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0500] R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it;

[0501] each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

[0502] W is alkylene or substituted alkylene containing 2 or more carbonatoms;

[0503] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6, or an olefin of the formula R¹⁷CH═CHR¹⁷;

[0504] each R¹⁷ is independently hydrogen, saturated hydrocarbyl orsubstituted saturated hydrocarbyl; and

[0505] X is a weakly coordinating anion;

[0506] and provided that when M is Ni, W is alkylene and each R¹⁷ isindependently hydrogen or saturated hydrocarbyl.

[0507] This invention also includes a process for the production of acompound of the formula

[0508] comprising, heating a compound of the formula

[0509] at a temperature of about −30° C. to about +100° for a sufficienttime to produce (XXXVIII); and wherein:

[0510] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substitutedk hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0511] R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it;

[0512] each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

[0513] R⁵⁶ is alkyl containing 2 to 30 carbon atoms;

[0514] T⁵ is alkyl;

[0515] W is alkylene containing 2 to 30 carbon atoms;

[0516] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6; and

[0517] X is a weakly coordinating anion.

[0518] This invention also concerns a process for the polymerization ofolefins, comprising, contacting a compound of the formula

[0519] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,

[0520] wherein:

[0521] R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

[0522] R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it;

[0523] each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

[0524] W is alkylene or substituted alkylene containing 2 or more carbonatoms;

[0525] Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6, or an olefin of the formula R¹⁷CH═CHR¹⁷;

[0526] each R¹⁷ is independently hydrogen, saturated hydrocarbyl orsubstituted saturated hydrocarbyl; and

[0527] X is a weakly coordinating anion;

[0528] and provided that:

[0529] when M is Ni, W is alkylene and each R¹⁷ is independentlyhydrogen or saturated hydrocarbyl;

[0530] and when norbornene or substituted norbornene is present, noother monomer is present.

[0531] This invention also concerns a homopolypropylene containing about10 to about 700 δ+ methylene groups per 1000 total methylene groups insaid homopolypropylene.

[0532] Described herein is a homopolypropylene wherein the ratio of δ+:γmethylene groups is about 0.5 to about 7.

[0533] Also included herein is a homopolypropylene in which about 30 toabout 85 mole percent of the monomer units are enchained in an ω,1fashion.

DETAILS OF THE INVENTION

[0534] Herein certain terms are used to define certain chemical groupsor compounds. These terms are defined below.

[0535] A “hydrocarbyl group” is a univalent group containing only carbonand hydrogen. If not otherwise stated, it is preferred that hydrocarbylgroups herein contain 1 to about 30 carbon atoms.

[0536] By “not containing olefinic or acetylenic bonds” is meant thegrouping does not contain olefinic carbon-carbon double bonds (butaromatic rings are not excluded) and carbon-carbon triple bonds.

[0537] By “substituted hydrocarbyl” herein is meant a hydrocarbyl groupwhich contains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbyl groups herein contain 1 to about 30 carbonatoms. Included in the meaning of “substituted” are heteroaromaticrings.

[0538] By an alkyl aluminum compound is meant a compound in which atleast one alkyl group is bound to an aluminum atom. Other groups such asalkoxide, oxygen, and halogen may also be bound to aluminum atoms in thecompound.

[0539] By “hydrocarbylene” herein is meant a divalent group containingonly carbon and hydrogen. Typical hydrocarbylene groups are —(CH₂)₄—,—CH₂CH(CH₂CH₃)CH₂CH₂— and

[0540] If not otherwise stated, it is preferred that hydrocarbylenegroups herein contain 1 to about 30 carbon atoms.

[0541] By “substituted hydrocarbylene” herein is meant a hydrocarbylenegroup which contains one or more substituent groups which are inertunder the process conditions to which the compound containing thesegroups is subjected. The substituent groups also do not substantiallyinterfere with the process. If not otherwise stated, it is preferredthat substituted hydrocarbylene groups herein contain 1 to about 30carbon atoms. Included within the meaning of “substituted” areheteroaromatic rings.

[0542] By substituted norbornene is meant a norbornene which issubstituted with one or more groups which does not interferesubstantially with the polymerization. It is preferred that substituentgroups (if they contain carbon atoms) contain 1 to 30 carbon atoms.Examples of substituted norbornenes are ethylidene norbornene andmethylene norbornene.

[0543] By “saturated hydrocarbyl” is meant a univalent group containingonly carbon and hydrogen which contains no unsaturation, such asolefinic, acetylenic, or aromatic groups. Examples of such groupsinclude alkyl and cycloalkyl. If not otherwise stated, it is preferredthat saturated hydrocarbyl groups herein contain 1 to about 30 carbonatoms.

[0544] By “neutral Lewis base” is meant a compound, which is not an ion,which can act as a Lewis base. Examples of such compounds includeethers, amines, sulfides, and organic nitriles.

[0545] By “cationic Lewis acid” is meant a cation which can act as aLewis acid. Examples of such cations are sodium and silver cations.

[0546] By “α-olefin” is meant a compound of the formula CH₂═CHR¹⁹,wherein R¹⁹ is n-alkyl or branched alkyl, preferably n-alkyl.

[0547] By “linear α-olefin” is meant a compound of the formulaCH₂═CHR¹⁹, wherein R¹⁹ is n-alkyl. It is preferred that the linearα-olefin have 4 to 40 carbon atoms.

[0548] By a “saturated carbon atom” is meant a carbon atom which isbonded to other atoms by single bonds only. Not included in saturatedcarbon atoms are carbon atoms which are part of aromatic rings.

[0549] By a quaternary carbon atom is meant a saturated carbon atomwhich is not bound to any hydrogen atoms. A preferred quaternary carbonatom is bound to four other carbon atoms.

[0550] By an olefinic bond is meant a carbon-carbon double bond, butdoes not include bonds in aromatic rings.

[0551] By a rare earth metal is meant one of lanthanum, cerium,praeseodymium, neodymium, promethium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

[0552] This invention concerns processes for making polymers,comprising, contacting one or more selected olefins or cycloolefins, andoptionally an ester or carboxylic acid of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, and other selected monomers, with a transitionmetal containing catalyst (and possibly other catalyst components). Suchcatalysts are, for instance, various complexes of a diimine with thesemetals. By a “polymerization process herein (and the polymers madetherein)” is meant a process which produces a polymer with a degree ofpolymerization (DP) of about 20 or more, preferably about 40 or more[except where otherwise noted, as in P in compound (VI)] By “DP” ismeant the average number of repeat (monomer) units in the polymer.

[0553] One of these catalysts may generally be written as

[0554] wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; Q is alkyl,hydride, chloride, iodide, or bromide; and S is alkyl, hydride,chloride, iodide, or bromide. Preferably M is Ni(II) or Pd(II).

[0555] In a preferred form of (I), R³ and R⁴ are each independentlyhydrogen or hydrocarbyl. If Q and/or S is alkyl, it is preferred thatthe alkyl contains 1 to 4 carbon atoms, and more preferably is methyl.

[0556] Another useful catalyst is

[0557] wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; T¹ is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; Z is aneutral Lewis base wherein the donating atom is nitrogen, sulfur oroxygen, provided that, if the donating atom is nitrogen, then the pKa ofthe conjugate acid of that compound is less than about 6; X is a weaklycoordinating anion; and R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds.

[0558] In one preferred form of (II), R³ and R⁴ are each independentlyhydrogen or hydrocarbyl. In a more preferred form of (II), T¹ is alkyl,and T¹ is especially preferably methyl. It is preferred that Z is R⁶ ₂Oor R⁷CN, wherein each R⁶ is independently hydrocarbyl and R⁷ ishydrocarbyl. It is preferred that R⁶ and R⁷ are alkyl, and it is morepreferred that they are methyl or ethyl. It is preferred that X⁻ is BAF,SbF₆, PF₆ or BF₄.

[0559] Another useful catalyst is

[0560] wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, or substitutedhydrocarbylene, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; T¹ is hydrogen, hydrocarbylnot containing olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵C(═O)—; Zis a neutral Lewis base wherein the donating atom is nitrogen, sulfur oroxygen, provided that if the donating atom is nitrogen then the pKa ofthe conjugate acid of that compound is less than about 6; X is a weaklycoordinating anion; and R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds.

[0561] In one preferred form of (III), R³ and R⁶ are each independentlyhydrogen, hydrocarbyl. In a more preferred form of (III) T¹ is alkyl,and T¹ is especially preferably methyl. It is preferred that Z is R⁶ ₂Oor R⁷CN, wherein each R⁶ is independently hydrocarbyl and R⁷ ishydrocarbyl. It is preferred that R⁶ and R⁷ are alkyl, and it isespecially preferred that they are methyl or ethyl. It is preferred thatX⁻ is BAF⁻, SbF₆ ⁻, PF₆ ⁻ or BF₄ ⁻.

[0562] Relatively weakly coordinating anions are known to the artisan.Such anions are often bulky anions, particularly those that maydelocalize their negative charge. Suitable weakly coordinating anions inthis Application include (Ph)₄B⁻ (Ph═phenyl),tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (herein abbreviated BAF),PF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, trifluoromethanesulfonate, p-toluenesulfonate,(R^(f)SO₂)₂N⁻, and (C₆F₅)₄B⁻. Preferred weakly coordinating anionsinclude BAF⁻, PF₆ ⁻, BF₄ ⁻, and SbF₆ ⁻.

[0563] Also useful as a polymerization-catalyst is a compound of theformula

[0564] wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; M is Ni(II) or Pd(II); each R¹⁶ isindependently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1,2, or 3; X is a weakly coordinating anion; and R⁸ is hydrocarbyl.

[0565] It is preferred that n is 3, and all of R¹⁶ are hydrogen. It isalso preferred that R⁸ is alkyl or substituted alkyl, especiallypreferred that it is alkyl, and more preferred that R⁸ is methyl.

[0566] Another useful catalyst is

[0567] wherein: R² and R⁵ are hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; T¹ is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl notcontaining olefinic or acetylenic bonds; E is halogen or —OR¹⁸; R¹⁸ ishydrocarbyl not containing olefinic or acetylenic bonds; and X is aweakly coordinating anion. It is preferred that T¹ is alkyl containing 1to 4 carbon atoms, and more preferred that it is methyl. In otherpreferred compounds (V), R³ and R⁴ are methyl or hydrogen and R² andR⁵are 2,6-diisopropylphenyl and X is BAF. It is also preferred that E ischlorine.

[0568] Another useful catalyst is a compound of the formula

[0569] wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; T² is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, hydrocarbyl substituted withketo or ester groups but not containing olefinic or acetylenic bonds,R¹⁵C(═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds; and X is a weakly coordinating anion. In a morepreferred form of (VII), T² is alkyl containing 1 to 4 carbon atoms andT² is especially preferably methyl. It is preferred that X isperfluoroalkylsulfonate, especially trifluoromethanesulfonate(triflate). If X⁻ is an extremely weakly coordinating anion such as BAF,(VII) may not form. Thus it may be said that (VII) forms usually withweakly, but perhaps not extremely weakly, coordinating anions.

[0570] In all compounds, intermediates, catalysts, processes, etc. inwhich they appear it is preferred that R² and R⁵ are each independentlyhydrocarbyl, and in one form it is especially preferred that R² and R⁵are both 2,6-diisopropylphenyl, particularly when R³ and R⁴ are eachindependently hydrogen or methyl. It is also preferred that R³ and R⁴are each independently hydrogen, hydrocarbyl or taken togetherhydrocarbylene to form a carbocyclic ring.

[0571] Compounds of the formula (I) wherein M is Pd, Q is alkyl and S ishalogen may be made by the reaction of the corresponding1,5-cyclooctadiene (COD) Pd complex with the appropriate diimine. When Mis Ni, (I) can be made by the displacement of a another ligand, such asa dialkylether or a polyether such as 1,2-dimethoxyethane, by anappropriate diimine.

[0572] Catalysts of formula (II), wherein X⁻ is BAF⁻, may be made byreacting a compound of formula (I) wherein Q is alkyl and S is halogen,with about one equivalent of an alkali metal salt, particularly thesodium salt, of HBAF, in the presence of a coordinating ligand,particularly a nitrile such as acetonitrile. When X⁻ is an anion such asBAF⁻, SbF₆ ⁻ or BF₄ ⁻ the same starting palladium compound can bereacted with the silver salt AgX.

[0573] However, sometimes the reaction of a diimine with a 1,5-COD Pdcomplex as described above to make compounds of formula (II) may be slowand/or give poor conversions, thereby rendering it difficult to make thestarting material for (II) using the method described in the precedingparagraph. For instance when: R²═R⁵═Ph₂CH— and R³═R⁴═H; R²═R⁵═Ph— andR³═R⁴═Ph; R²═R⁵═2-t-butylphenyl and R³═R⁴═CH₃; R²═R⁵═α-naphthyl andR³═R⁴═CH₃; and R²═R⁵═2-phenylphenyl and R³═R⁴═CH₃ difficulty may beencountered in making a compound of formula (II).

[0574] In these instances it has been found more convenient to prepare(II) by reacting [(η⁴-1,5-COD)PdT¹Z]⁺X⁻, wherein T¹ and X are as definedabove and Z is an organic nitrile ligand, preferably in an organicnitrile solvent, with a diimine of the formula

[0575] By a “nitrile solvent” is meant a solvent that is at least 20volume percent nitrile compound. The product of this reaction is (II),in which the Z ligand is the nitrile used in the synthesis. In apreferred synthesis, T¹ is methyl and the nitrile used is the same as inthe starting palladium compound, and is more preferably acetonitrile.The process is carried out in solution, preferably when the nitrile issubstantially all of the solvent, at a temperature of about −40° C. toabout +60° C., preferably about 0° C. to about 30° C. It is preferredthat the reactants be used in substantially equimolar quantities.

[0576] The compound [(η⁴-1,5-COD)PdT¹Z]⁺X⁻, wherein T¹ is alkyl, Z is anorganic nitrile and X is a weakly coordinating anion may be made by thereaction of [(η⁴-1,5-COD)PdT¹A, wherein A is Cl, Br or I and T¹ is alkylwith the silver salt of X⁻, AgX, or if X is BAF with an alkali metalsalt of HBAF, in the presence of an organic nitrile, which of coursewill become the ligand T¹. In a preferred process A is Cl, T¹ is alkyl,more preferably methyl, and the organic nitrile is an alkyl nitrile,more preferably acetonitrile. The starting materials are preferablypresent in approximately equimolar amounts, except for the nitrile whichis present preferably in excess. The solvent is preferably anon-coordinating solvent such as a halocarbon. Methylene chloride isuseful as such a solvent. The process preferably is carried out at atemperature of about −40° C. to about +50° C. It is preferred to excludewater and other hydroxyl containing compounds from the process, and thismay be done by purification of the ingredients and keeping the processmass under an inert gas such as nitrogen.

[0577] Compounds of formula (II) [or (III) when the metal is nickel] canalso be made by the reaction of

[0578] with a source of the conjugate acid of the anion X, the acid HXor its equivalent (such as a trityl salt) in the presence of a solventwhich is a weakly coordinating ligand such as a dialkyl ether or analkyl nitrile. It is preferred to carry out this reaction at about −80°C. to about 30° C.

[0579] Compounds of formula (XXXXI) can be made by a process,comprising, contacting, at a temperature of about −80° C. to about +20°C., a compound of the formula (η⁴-1,5-COD)PdMe₂ and a diimine of theformula

[0580] wherein: COD is 1,5-cyclooctadiene; R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring. It ispreferred that the temperature is about −50° C. to about +10° C. It isalso preferred that the two starting materials be used in approximatelyequimolar quantities, and/or that the reaction be carried out insolution. It is preferred that R² and R⁵ are both 2-t-butylphenyl or2,5-di-t-butylphenyl and that R³ and R⁴ taken together are An, or R³ andR⁴ are both hydrogen or methyl.

[0581] Compounds of formula (IV) can be made by several routes. In onemethod a compound of formula (II) is reacted with an acrylate ester ofthe formula CH₂═CHCO₂R¹ wherein R¹ is as defined above. This reaction iscarried out in a non-coordinating solvent such as methylene chloride,preferably using a greater than 1 to 50 fold excess of the acrylateester. In a preferred reaction, Q is methyl, and R¹ is alkyl containing1 to 4 carbon atoms, more preferably methyl. The process is carried outat a temperature of about −100° C. to about +100° C., preferably about0° C. to about 50° C. It is preferred to exclude water and otherhydroxyl containing compounds from the process, and this may be done bypurification of the ingredients and keeping the process mass under aninert gas such as nitrogen

[0582] Alternatively, (IV) may be prepared by reacting (I), wherein Q isalkyl and S is Cl, Br or I with a source of an appropriate weaklycoordinating anion such as AgX or an alkali metal salt of BAF and anacrylate ester (formula as immediately above) in a single step.Approximately equimolar quantities of (I) and the weakly coordinatinganion source are preferred, but the acrylate ester may be present ingreater than 1 to 50 fold excess. In a preferred reaction, Q is methyl,and R¹ is alkyl containing 1 to 4 carbon atoms, more preferably methyl.The process is preferably carried out at a temperature of about −100° C.to about +100° C., preferably about 0° C. to about 50° C. It ispreferred to exclude water and other hydroxyl containing compounds fromthe process, and this may be done by purification of the ingredients andkeeping the process mass under an inert gas such as nitrogen.

[0583] In another variation of the preparation of (IV) from (I) thesource of the weakly coordinating anion is a compound which itself doesnot contain an anion, but which can combine with S [of (I)] to form sucha weakly coordinating anion. Thus in this type of process by “source ofweakly coordinating anion” is meant a compound which itself contains theanion which will become X⁻, or a compound which during the process cancombine with other process ingredients to form such an anion.

[0584] Catalysts of formula (V), wherein X⁻ is BAF⁻, may be made byreacting a compound of formula (I) wherein Q is alkyl and S is halogen,with about one-half of an equivalent of an alkali metal salt,particularly the sodium salt, of HBAF. Alternatively, (V) containingother anions may be prepared by reacting (I), wherein Q is alkyl and Sis Cl, Br or I with one-half equivalent of a source of an appropriateweakly coordinating anion such as AgX.

[0585] Some of the nickel and palladium compounds described above areuseful in processes for polymerizing various olefins, and optionallyalso copolymerizing olefinic esters, carboxylic acids, or otherfunctional olefins, with these olefins. When (I) is used as a catalyst,a neutral Lewis acid or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion is also present as part of thecatalyst system (sometimes called a “first compound” in the claims). Bya “neutral Lewis acid” is meant a compound which is a Lewis acid capablefor abstracting Q⁻ or S⁻ from (I) to form a weakly coordination anion.The neutral Lewis acid is originally uncharged (i.e., not ionic).Suitable neutral Lewis acids include SbF₅, Ar₃B (wherein Ar is aryl),and BF₃. By a cationic Lewis acid is meant a cation with a positivecharge such as Ag⁺, H⁺, and Na⁺.

[0586] In those instances in which (I) (and similar catalysts whichrequire the presence of a neutral Lewis acid or a cationic Lewis orBronsted acid), does not contain an alkyl or hydride group alreadybonded to the metal (i.e., neither Q or S is alkyl or hydride), theneutral Lewis acid or a cationic Lewis or Bronsted acid also alkylatesor adds a hydride to the metal, i.e., causes an alkyl group or hydrideto become bonded to the metal atom.

[0587] A preferred neutral Lewis acid, which can alkylate the metal, isa selected alkyl aluminum compound, such as R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlCl₂,and “R⁹AlO” (alkylaluminoxanes), wherein R⁹ is alkyl containing 1 to 25carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminumcompounds include methylaluminoxane (which is an oligomer with thegeneral formula [MeAlO]_(n)), (C₂H₅)₂AlCl, C₂H₅AlCl₂, and[(CH₃)₂CHCH₂]₃Al.

[0588] Metal hydrides such as NaBH₄ may be used to bond hydride groupsto the metal M.

[0589] The first compound and (I) are contacted, usually in the liquidphase, and in the presence of the olefin, and/or 4-vinylcyclohexene,cyclopentene, cyclobutene, substituted norbornene, or norbornene. Theliquid phase may include a compound added just as a solvent and/or mayinclude the monomer(s) itself. The molar ratio of first compound:nickelor palladium complex is about 5 to about 1000, preferably about 10 toabout 100. The temperature at which the polymerization is carried out isabout −100° C. to about +200° C., preferably about −20° C. to about +80°C. The pressure at which the polymerization is carried out is notcritical, atmospheric pressure to about 275 MPa, or more, being asuitable range. The pressure may affect the microstructure of thepolyolefin produced (see below).

[0590] When using (I) as a catalyst, it is preferred that R³ and R⁴ arehydrogen, methyl, or taken together are

[0591] It is also preferred that both R² and R⁵ are2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl,4-methylphenyl, phenyl, 2,4,6-trimethylphenyl, and 2-t-butylphenyl. WhenM is Ni(II), it is preferred that Q and S are each independentlychloride or bromide, while when M is Pd(II) it is preferred that Q ismethyl, chloride, or bromide, and S is chloride, bromide or methyl. Inaddition, the specific combinations of groups in the catalysts listed inTable I are especially preferred. TABLE I R² R³ R⁵ R⁵ Q S M 2,6-i-PrPh HH 2,6-i-PrPh Me Cl Pd 2,6-i-PrPh Me Me 2,6-i-PrPh Me Cl Pd 2,6-i-PrPh AnAn 2,6-i-PrPh Me Cl Pd 2,6-MePh H H 2,6-MePh Me Cl Pd 4-MePh H H 4-MePhMe Cl Pd 4-MePh Me Me 4-MePh Me Cl Pd 2,6-i-PrPh Me Me 2,6-i-PrPh Me MePd 2,6-i-PrPh H H 2,6-i-PrPh Me Me Pd 2,6-MePh H H 2,6-MePh Me Me Pd2,6-i-PrPh H H 2,6-i-PrPh Br Br Ni 2,6-i-PrPh Me Me 2,6-i-PrPh Br Br Ni2,6-MePh H H 2,6-MePh Br Br Ni Ph Me Me Ph Me Cl Pd 2,6-EtPh Me Me2,6-EtPh Me Cl Pd 2,4,6-MePh Me Me 2,4,6-MePh Me Cl Pd 2,6-MePh Me Me2,6-MePh Br Br Ni 2,6-i-PrPh An An 2,6-i-PrPh Br Br Ni 2,6-MePh An An2,6-MePh Br Br Ni 2-t-BuPh An An 2-t-BuPh Br Br Ni 2,5-t-BuPh An An2,5-t-BuPh Br Br Ni 2-i-Pr-6-MePh An An 2-i-Pr-6-MePh Br Br Ni2-i-Pr-6-MePh Me Me 2-i-Pr-6-MePh Br Br Ni 2,6-t-BuPh H H 2,6-t-BuPh BrBr Ni 2,6-t-BuPh Me Me 2,6-t-BuPh Br Br Ni 2,6-t-BuPh An An 2,6-t-BuPhBr Br Ni 2-t-BuPh Me Me 2-t-BuPh Br Br Ni # Np = naphthyl; An =1,8-naphthylylene (a divalent radical used for both R³ and R⁴, whereinR³ and R⁴ taken together form a ring, which is part of an acenaphthylenegroup); OTf = triflate; and BAF =tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

[0592] Preferred olefins in the polymerization are one or more ofethylene, propylene, 1-butene, 2-butene, 1-hexene 1-octene, 1-pentene,1-tetradecene, norbornene, and cyclopentene, with ethylene, propyleneand cyclopentene being more preferred. Ethylene (alone as a homopolymer)is especially preferred.

[0593] The polymerizations with (I) may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The catalystsystem, monomer(s), and polymer may be soluble or insoluble in theseliquids, but obviously these liquids should not prevent thepolymerization from occurring. Suitable liquids include alkanes,cycloalkanes, selected halogenated hydrocarbons, and aromatichydrocarbons. Specific useful solvents include hexane, toluene andbenzene.

[0594] Whether such a liquid is used, and which and how much liquid isused, may affect the product obtained. It may affect the yield,microstructure, molecular weight, etc., of the polymer obtained.

[0595] Compounds of formulas (XI), (XIII), (XV) and (XIX) may also beused as catalysts for the polymerization of the same monomers ascompounds of formula (I). The polymerization conditions are the same for(XI), (XIII), (XV) and (XIX) as for (I), and the same Lewis and Bronstedacids are used as co-catalysts. Preferred groupings R², R³, R⁴, and R⁵(when present) in (XI) and (XIII) are the same as in (I), both in apolymerization process and as compounds in their own right.

[0596] Preferred (XI) compounds have the metals Sc(III), Zr(IV), Ni(II),Ni(I), Pd(II), Fe(II), and Co(II). When M is Zr, Ti, Fe, and Sc it ispreferred that all of Q and S are chlorine or bromine more preferablychlorine. When M is Ni or Co it is preferred that all of Q and S arechlorine, bromine or iodine, more preferably bromine.

[0597] In (XVII) preferred metals are Ni(II) and Ti(IV). It is preferredthat all of Q and S are halogen. It is also preferred that all of R²⁸,R²⁹, and R³⁰ are hydrogen, and/or that both R⁴⁴ and R⁴⁵ are2,4,6-trimethylphenyl or 9-anthracenyl.

[0598] In (XV) it is preferred that both of R³¹ are hydrogen.

[0599] In (XIII), (XXIII) and (XXXII) (as polymerization catalysts andas novel compounds) it is preferred that all of R²⁰, R²¹, R²² and R²³are methyl. It is also preferred that T¹ and T² are methyl. For (XIII),when M is Ni(I) or (II), it is preferred that both Q and S are bromine,while when M is Pd it is preferred that Q is methyl and S is chlorine.

[0600] Compounds (II), (IV) or (VII) will each also cause thepolymerization of one or more of an olefin, and/or a selected cyclicolefin such as cyclobutene, cyclopentene or norbornene, and, when it isa Pd(II) complex, optionally copolymerize an ester or carboxylic acid ofthe formula CH₂═CH(CH₂)_(m)CO₂R¹, wherein m is 0 or an integer of 1 to16 and R¹ is hydrogen or hydrocarbyl or substituted hydrocarbyl, bythemselves (without cocatalysts). However, (III) often cannot be usedwhen the ester is present. When norbornene or substituted norbornene ispresent no other monomer should be present.

[0601] Other monomers which may be used with compounds (II), (IV) or(VII) (when it is a Pd(II) complex) to form copolymers with olefins andselected cycloolefins are carbon monoxide (CO), and vinyl ketones of thegeneral formula H₂C═CHC(O)R²⁵, wherein R²⁵ is alkyl containing 1 to 20carbon atoms, and it is preferred that R²⁵ is methyl. In the case of thevinyl ketones, the same compositional limits on the polymers producedapply as for the carboxylic acids and esters described as comonomers inthe immediately preceding paragraph.

[0602] CO forms alternating copolymers with the various olefins andcycloolefins which may be polymerized with compounds (II), (IV) or(VII). The polymerization to form the alternating copolymers is donewith both CO and the olefin simultaneously in the process mixture, andavailable to the catalyst. It is also possible to form block copolymerscontaining the alternating CO/(cyclo)olefin copolymers and other blockscontaining just that olefin or other olefins or mixtures thereof. Thismay be done simply by sequentially exposing compounds (II), (IV) or(VII), and their subsequent living polymers, to the appropriate monomeror mixture of monomers to form the desired blocks. Copolymers of CO, a(cyclo)olefin and a saturated carboxylic acid or ester of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein m is 0 or an integer of 1 to 16 and R¹ ishydrogen or hydrocarbyl or substituted hydrocarbyl, may also be made bysimultaneously exposing the polymerization catalyst or living polymer tothese 3 types of monomers.

[0603] The polymerizations may be carried out with (II), (III), (IV) or(VII), and other catalyst molecules or combinations, initially in thesolid state [assuming (II), (III) (IV) or (VII) is a solid] or insolution. The olefin and/or cycloolefin may be in the gas or liquidstate (including gas dissolved in a solvent). A liquid, which may or maynot be a solvent for any or all of the reactants and/or products mayalso be present. Suitable liquids include alkanes, cycloalkanes,halogenated alkanes and cycloalkanes, ethers, water, and alcohols,except that when (III) is used, hydrocarbons should preferably be usedas solvents. Specific useful solvents include methylene chloride,hexane, CO₂, chloroform, perfluoro(n-butyltetrahydrofuran) (hereinsometimes called FC-75), toluene, dichlorobenzene, 2-ethylhexanol, andbenzene.

[0604] It is particularly noteworthy that one of the liquids which canbe used in this polymerization process with (II), (III), (IV) or (VII)is water, see for instance Examples 213-216. Not only can water bepresent but the polymerization “medium” may be largely water, andvarious types of surfactants may be employed so that an emulsionpolymerization may be done, along with a suspension polymerization whensurfactants are not employed.

[0605] Preferred olefins and cycloolefins in the polymerization using(II), (III) or (IV) are one or more of ethylene, propylene, 1-butene,1-hexene, 1-octene, 1-butene, cyclopentene, 1-tetradecene, andnorbornene; and ethylene, propylene and cyclopentene are more preferred.Ethylene alone is especially preferred.

[0606] Olefinic esters or carboxylic acids of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen, hydrocarbyl, orsubstituted hydrocarbyl, and m is 0 or an integer of 1 to 16. It ispreferred if R¹ hydrocarbyl or substituted hydrocarbyl and it is morepreferred if it is alkyl containing 1 to 10 carbon atoms, or glycidyl.It is also preferred if m is 0 and/or R¹ is alkyl containing 1 to 10carbon atoms. It is preferred to make copolymers containing up to about60 mole percent, preferably up to about 20 mole percent of repeat unitsderived from the olefinic ester or carboxylic acid. Total repeat unitunits in the polymer herein refer not only to those in the main chainfrom each monomer unit, but those in branches or side chains as well.

[0607] When using. (II), (III), (IV) or (VII) as a catalyst it ispreferred that R³ and R⁴ are hydrogen, methyl, or taken together are

[0608] It is also preferred that both R² and R⁵ are2,6-diisopropylphenyl, 2,6-dimethylphenyl, 4-methylphenyl, phenyl,2,6-diethylphenyl, 2,4,6-trimethylphenyl and 2-t-butylphenyl. When (II)is used, it is preferred that T¹ is methyl, R⁶ is methyl or ethyl and R⁷is methyl. When (III) is used it is preferred that T¹ is methyl and saidLewis base is R⁶ ₂O, wherein R⁶ is methyl or ethyl. When (IV) is used itis preferred that R⁸ is methyl, n is 3 and R¹⁶ is hydrogen. In additionin Table II are listed all particularly preferred combinations ascatalysts for (II), (III), (IV) and (VII). TABLE II Com- T¹/ pound T²/Type R² R³ R⁴ R⁵ R⁸ Z M X (II) 2,6-i- Me Me 2,6-i- Me OEt₂ Pd BAF PrPhPrPh (II) 2,6-i- H H 2,6-i- Me OEt₂ Pd BAF PrPh PrPh (III) 2,6-i- Me Me2,6-i- Me OEt₂ Ni BAF PrPh PrPh (III) 2,6-i- H H 2,6-i- Me OEt₂ Ni BAFPrPh PrPh (II) 2,6- H H 2,6-MePh Me OEt₂ Pd BAF MePh (II) 2,6- Me Me2,6-MePh Me OEt₂ Pd BAF MePh (II) 2,6-i- Me Me 2,6-i- Me OEt₂ Pd SbF₆PrPh PrPh (II) 2,6-i- Me Me 2,6-i- Me OEt₂ Pd BF₄ PrPh PrPh (II) 2,6-i-Me Me 2,6-i- Me OEt₂ Pd PF₆ PrPh PrPh (II) 2,6-i- H H 2,6-i- Me OEt₂ PdSbF₆ PrPh PrPh (II) 2,4,6- Me Me 2,4,6- Me OEt₂ Pd SbF₆ MePh MePh (II)2,6-i- An An 2,6-i- Me OEt₂ Pd SbF₆ PrPh PrPh (II) 2,6-i- Me Me 2,6-i-Me NCMe Pd SbF₆ PrPh PrPh (II) Ph Me Me Ph Me NCMe Pd SbF₆ (II) 2,6- MeMe 2,6-EtPh Me NCMe Pd BAF EtPh (II) 2,6- Me Me 2,6-EtPh Me NCMe Pd SbF₆EtPh (II) 2-t- Me Me 2-t-BuPh Me NCMe Pd SbF₆ BuPh (II) 1-Np Me Me 1-NpMe NCMe Pd SbF₆ (II) Ph₂CH H H Ph₂CH Me NCMe Pd SbF₆ (II) 2-PhPh Me Me2-PhPh Me NCMe Pd SbF₆ (II) Ph ^(a) ^(a) Ph Me NCMe Pd BAF (IV) 2,6-i-Me Me 2,6-i- Me ^(b) Pd SbF₆ PrPh PrPh (IV) 2,6-i- Me Me 2,6-i- Me ^(b)Pd BAF PrPh PrPh (IV) 2,6-i- H H 2,6-i- Me ^(b) Pd SbF₆ PrPh PrPh (IV)2,6-i- Me Me 2,6-i- Me ^(b) Pd B(C₆F₅)₃Cl PrPh PrPh (II) Ph Me Me Ph MeNCMe Pd SbF₆ (VII) 2,6-i- Me Me 2,6-i- Me — Pd OTf PrPh PrPh (II) Ph PhPh Ph Me NCMe Pd BAF (II) Ph₂CH H H Ph₂CH Me NCMe Pd SbF₆

[0609] When using (II), (III), (IV) or (VII) the temperature at whichthe polymerization is carried out is about −100° C. to about +200° C.,preferably about 0° C. to about 150° C., more preferably about 25° C. toabout 100° C. The pressure at which the polymerization is carried out isnot critical, atmospheric pressure to about 275 MPa being a suitablerange. The pressure can affect the microstructure of the polyolefinproduced (see below).

[0610] Catalysts of the formulas (II), (III), (IV) and (VII) may also besupported on a solid catalyst (as opposed to just being added as a solidor in solution), for instance on silica gel (see Example 98). Bysupported is meant that the catalyst may simply be carried physically onthe surface of the solid support, may be adsorbed, or carried by thesupport by other means.

[0611] When using (XXX) as a ligand or in any process or reaction hereinit is preferred that n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, andboth of R⁴⁴ and R⁴⁵ are 9-anthracenyl.

[0612] Another polymerization process comprises contacting a compound ofthe formula [Pd(R¹³CN)₄]X₂ or a combination of Pd[OC(O)R⁴⁰]₂ and HX,with a compound of the formula

[0613] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene and norbornene,wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided that R¹⁷ contains no olefinic bonds;R⁴⁰ is hydrocarbyl or substituted hydrocarbyl; and X is a weaklycoordinating anion; provided that when norbornene or substitutednorbornene is present no other monomer is present.

[0614] It is believed that in this process a catalyst similar to (II)may be initially generated, and this then causes the polymerization.Therefore, all of the conditions, monomers (including olefinic estersand carboxylic acids), etc., which are applicable to the process using(II) as a polymerization catalyst are applicable to this process. Allpreferred items are also the same, including appropriate groups such asR², R³, R⁴, R⁵, and combinations thereof. This process however should berun so that all of the ingredients can contact each other, preferably ina single phase. Initially at least, it is preferred that this is done insolution. The molar ratio of (VIII) to palladium compound used is notcritical, but for most economical use of the compounds, a moderateexcess, about 25 to 100% excess, of (VIII) is preferably used.

[0615] As mentioned above, it is believed that in the polymerizationusing (VIII) and [Pd(R¹³CN)₄]X₂ or a Pd[II] carboxylate a catalystsimilar to (II) is formed. Other combinations of starting materials thatcan combine into catalysts similar to (II), (III), (IV) and (VII) oftenalso cause similar polymerizations, see for instance Examples 238 and239. Also combinations of α-diimines or other diimino ligands describedherein with: a nickel [0] or nickel [I] compound, oxygen, an alkylaluminum compound and an olefin; a nickel [0] or nickel [I] compound, anacid such as HX and an olefin; or an α-diimine Ni[0] or nickel [I]complex, oxygen, an alkyl aluminum compound and an olefin. Thus activecatalysts from α-diimines and other bidentate imino compounds can beformed beforehand or in the same “pot” (in situ) in which thepolymerization takes place. In all of the polymerizations in which thecatalysts are formed in situ, preferred groups on the α-diimines are thesame as for the preformed catalysts.

[0616] In general Ni[0], Ni[I] or Ni(II) compounds may be used asprecursors to active catalyst species. They must have ligands which canbe displaced by the appropriate bidentate nitrogen ligand, or mustalready contain such a bidentate ligand already bound to the nickelatom. Ligands which may be displaced include 1,5-cyclooctadiene andtris(o-tolyl)phosphite, which may be present in Ni[0] compounds, ordibenzylideneacetone, as in the useful Pd[0] precursortris(dibenzylideneacetone)dipalladium[0]. These lower valence nickelcompounds are believed to be converted into active Ni[II] catalyticspecies. As such they must also be contacted (react with) with anoxidizing agent and a source of a weakly coordinating anion (X⁻).Oxidizing agents include oxygen, HX (wherein X is a weakly coordinatinganion), and other well known oxidizing agents. Sources of X⁻ include HX,alkylaluminum compounds, alkali metal and silver salts of X⁻. As can beseen above, some compounds such as HX may act as both an oxidizing agentand a source of X⁻. Compounds containing other lower valent metals maybe converted into active catalyst species by similar methods.

[0617] When contacted with an alkyl aluminum compound or HX useful Ni[0]compounds include

[0618] Various types of Ni[0] compounds are known in the literature.Below are listed references for the types shown immediately above.

[0619] (XXXIII) G. van Koten, et al., Adv. Organometal. Chem., vol. 21,p. 151-239 (1982).

[0620] (XXXXII) W. Bonrath, et al., Angew. Chem. Int. Ed. Engl., vol.29, p. 298-300 (1990).

[0621] (XXXXIV) H. tom Dieck, et al., Z. Natruforsch., vol. 366, p.823-832 (1981); and M. Svoboda, et al., J. Organometal. Chem., vol. 191,p. 321-328 (1980).

[0622] (XXXXV) G. van Koten, et al., Adv. Organometal. Chem., vol. 21,p. 151-239 (1982).

[0623] In polymerizations using (XIV), the same preferred monomers andgroups (such as R², R³, R⁴, R⁵ and X) as are preferred for thepolymerization using (II) are used and preferred. Likewise, theconditions used and preferred for polymerizations with (XIV) are similarto those used and preferred for (II), except that higher olefinpressures (when the olefin is a gas) are preferred. Preferred pressuresare about 2.0 to about 20 MPa. (XIV) may be prepared by the reaction ofone mole of [Pd(R¹³CN)₄]X₂ with one mole of (VIII) in acetonitrile ornitromethane.

[0624] Novel compound (XIV) is used as an olefin polymerizationcatalyst. In preferred forms of (XIV), the preferred groups R², R³, R⁴,R⁵ and X are the same as are preferred for compound (II).

[0625] Another type of compound which is an olefin polymerizationcatalyst are π-allyl and π-benzyl compounds of the formula

[0626] wherein M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; X is a weakly coordinatinganion; and A is a π-allyl or π-benzyl group. By a π-allyl group is meanta monoanionic with 3 adjacent sp² carbon atoms bound to a metal centerin an η³ fashion. The three Sp² carbon atoms may be substituted withother hydrocarbyl groups or functional groups. Typical η-allyl groupsinclude

[0627] wherein R is hydrocarbyl. By a π-benzyl group is meant π-allylligand in which two of the sp² carbon atoms are part of an aromaticring. Typical π-benzyl groups include

[0628] π-Benzyl compounds usually initiate polymerization of the olefinsfairly readily even at room temperature, but π-allyl compounds may notnecessarily do so. Initiation of π-allyl compounds can be improved byusing one or more of the following methods:

[0629] Using a higher temperature such as about 80° C.

[0630] Decreasing the bulk of the α-diimine ligand, such as R² and R⁵being 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.

[0631] Making the π-allyl ligand more bulky, such as using

[0632] rather than the simple π-allyl group itself.

[0633] Having a Lewis acid present while using a functional π-allyl orπ-benzyl group. Relatively weak Lewis acids such a triphenylborane,tris(pentafluorophenyl)borane, andtris(3,5-trifluoromethylphenyl)borane, are preferred. Suitablefunctional groups include chloro and ester. “Solid” acids such asmontmorillonite may also be used.

[0634] When using (XXXVII) as-a polymerization catalyst, it is preferredthat ethylene and/or a linear α-olefin is the monomer, or cyclopentene,more preferred if the monomer is ethylene and/or propylene, and ethyleneis especially preferred. A preferred temperature for the polymerizationprocess using (XXXVII) is about +20° C. to about 100° C. It is alsopreferred that the partial pressure due to ethylene or propylene monomeris at least about 600 kPa.It is also noted that (XXXVII) is a novelcompound, and preferred items for (XXXVII) for the polymerizationprocess are also preferred for the compound itself.

[0635] Another catalyst for the polymerization of olefins is a compoundof the formula

[0636] and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,

[0637] wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; R⁵⁴ is hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; eachR⁵⁵ is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, ora functional group; W is alkylene or substituted alkylene containing 2or more carbon atoms; Z is a neutral Lewis base wherein the donatingatom is nitrogen, sulfur, or oxygen, provided that if the donating atomis nitrogen then the pKa of the conjugate acid of that compound(measured in water) is less than about 6, or an olefin of the formulaR¹⁷CH═CHR¹⁷; each R¹⁷ is independently alkyl or substituted alkyl; and Xis a weakly coordinating anion. It is preferred that in compound(XXXVIII) that: R⁵⁴ is phenyl or substituted phenyl, and preferredsubstituents are alkyl groups; each R⁵⁵ is independently hydrogen oralkyl containing 1 to 10 carbon atoms; W contains 2 carbon atoms betweenthe phenyl ring and metal atom it is bonded to or W is a divalentpolymeric group derived from the polymerization of R¹⁷CH═CHR¹⁷, and itis especially preferred that it is —CH(CH₃)CH₂— or —C(CH₃)₂CH₂—; and Zis a dialkyl ether or an olefin of the formula R¹⁷CH═CHR¹⁷; andcombinations thereof. W is an alkylene group in which each of the twofree valencies are to different carbon atoms of the alkylene group.

[0638] When W is a divalent group formed by the polymerization ofR¹⁷CH═CHR¹⁷, and Z is R¹⁷CH═CHR¹⁷, the compound (XXXVIII) is believed tobe a living ended polymer. That end of W bound to the phenyl ringactually is the original fragment from R⁵⁶ from which the “bridge” Woriginally formed, and the remaining part of W is formed from theolefin(s) R¹⁷CH═CHR¹⁷. In a sense this compound is similar in functionto compound (VI).

[0639] By substituted phenyl in (XXXVIII) and (XXXIX) is meant thephenyl ring can be substituted with any grouping which does notinterfere with the compound's stability or any of the reactions thecompound undergoes. Preferred substituents in substituted phenyl arealkyl groups, preferably containing 1 to 10 carbon atoms.

[0640] Preferred monomers for this polymerization are ethylene andlinear α-olefins, or cyclopentene, particularly propylene, and ethyleneand propylene or both are more preferred, and ethylene is especiallypreferred.

[0641] It is noted that (XXXVIII) is a novel compound, and preferredcompounds and groupings are the same as in the polymerization process.

[0642] Compound (XXXVIII) can be made by heating compound (XXXIX),

[0643] wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; R⁵⁴ is hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; eachR⁵⁵ is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, ora functional group; R⁵⁶ is alkyl containing 2 to 30 carbon atoms; T³ isalkyl; Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6; and X is a weakly coordinating anion. Preferredgroups are the same as those in (XXXVIII). In addition it is preferredthat T⁵ contain 1 to 10 carbon atoms, and more preferred that it ismethyl. A preferred temperature for the conversion of (XXXIX) to(XXXVIII) is about −30° C. to about 50° C. Typically the reaction takesabout 10 min. to about 5 days, the higher the temperature, the fasterthe reaction. Another factor which affects the reaction rate is thenature of Z. The weaker the Lewis basicity of Z, the faster the desiredreaction will be.

[0644] When (II), (III), (IV), (V), (VII), (VIII) or a combination ofcompounds that will generate similar compounds, (subject to theconditions described above) is used in the polymerization of olefins,cyclolefins, and optionally olefinic esters or carboxylic acids, polymerhaving what is believed to be similar to a “living end” is formed. Thismolecule is that from which the polymer grows to its eventual molecularweight. This compound may have the structure

[0645] wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; each R¹¹ is independentlyhydrogen, alkyl or —(CH₂)_(m)CO₂R¹; T³ is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, R¹⁵(C═O)—, R¹⁵O(C═O)—, or—CH₂CH₂CH₂CO₂R⁸; R¹⁵ is hydrocarbyl not containing olefinic oracetylenic unsaturation; P is a divalent group containing one or morerepeat units derived from the polymerization of one or more of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, or norbornene and, when M isPd(II), optionally one or more compounds of the formulaCH₂═CH(CH₂)_(m)CO₂R¹; R⁸ is hydrocarbyl; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;m is 0 or an integer from 1 to 16; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms; and X is aweakly coordinating anion; and that when M is Ni(II), R is not —CO₂R⁸and when M is Pd a diene is not present. By an “olefinic ester orcarboxylic acid” is meant a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein m and R¹ are as defined immediately above.

[0646] This molecule will react with additional monomer (olefin, cyclicolefin, olefinic ester or olefinic carboxylic acid) to cause furtherpolymerization. In other words, the additional monomer will be added toP, extending the length of the polymer chain. Thus P may be of any size,from one “repeat unit” to many repeat units, and when the polymerizationis over and P is removed from M, as by hydrolysis, P is essentially thepolymer product of the polymerization. Polymerizations with (VI), thatis contact of additional monomer with this molecule takes place underthe same conditions as described above for the polymerization processusing (II), (III), (IV), (V), (VII) or (VIII), or combinations ofcompounds that will generate similar molecules, and where appropriatepreferred conditions and structures are the same.

[0647] The group T³ in (VI) was originally the group T¹ in (II) or(III), or the group which included R⁸ in (IV). It in essence willnormally be one of the end groups of the eventual polymer product. Theolefinic group which is coordinated to M, R¹¹CH═CHR¹¹ is normally one ofthe monomers, olefin, cyclic olefin, or, if Pd(II) is M, an olefinicester or carboxylic acid. If more than one of these monomers is presentin the reaction, it may be any one of them. It is preferred that T³ isalkyl and especially preferred that it is methyl, and it is alsopreferred that R¹¹ is hydrogen or n-alkyl. It is also preferred that Mis Pd(II).

[0648] Another “form” for the living end is (XVI).

[0649] This type of compound is sometimes referred to as a compound inthe “agostic state”. In fact both (VI) and (XVI) may coexist together inthe same polymerization, both types of compound representing livingends. It is believed that (XVI)-type compounds are particularly favoredwhen the end of the growing polymer chain bound to the transition metalis derived from a cyclic olefin such as cyclopentene. Expressed in termsof the structure of (XVI) this is when both of R¹¹ are hydrocarbylene toform a carbocyclic ring, and it is preferred that this be afive-membered carbocyclic ring.

[0650] For both the polymerization process using (XVI) and the structureof (XVI) itself, the same conditions and groups as are used andpreferred for (VI) are also used and preferred for (XVI), with theexception that for R¹¹ it is preferred in (XVI) that both of R¹¹ arehydrocarbylene to form a carbocyclic ring.

[0651] This invention also concerns a compound of the formula

[0652] wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R and R taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; each R¹⁴ is independently hydrogen, alkylor [when M is Pd(II)] —(CH₂)_(m)CO₂R¹; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms; T⁴ is alkyl,—R⁶⁰C(O)OR⁸, R¹⁵(C═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl not containingolefinic or acetylenic bonds; R⁶⁰ is alkylene not containing olefinic oracetylenic bonds; R⁸ is hydrocarbyl; and X is a weakly coordinatinganion.

[0653] (IX) may also be used to polymerize olefins, cyclic olefins, andoptionally olefinic esters and carboxylic acids. The same conditions(except as noted below) apply to the polymerizations using (IX) as theydo for (VI). It is preferred that M is Pd(II) and T⁴ is methyl.

[0654] A compound of formula (V) may also be used as a catalyst for thepolymerization of olefins, cyclic olefins, and optionally olefinicesters and/or carboxylic acids. In this process (V) is contacted withone or more of the essential monomers. Optionally a source of arelatively weakly coordinating anion may also be present. Such a sourcecould be an alkali metal salt of BAF or AgX (wherein X is the anion),etc. Preferably about 1 mole of the source of X, such as AgX, will beadded per mole of (V). This will usually be done in the liquid phase,preferably in which (V) and the source of the anion are at leastpartially soluble. The conditions of this polymerization are otherwisethe same as described above for (II), (III), (IV) and (VII), includingthe preferred conditions and ingredients.

[0655] In polymerizations using (XX) as the catalyst, a first compoundwhich is a source of a relatively noncoordinating monoanion is present.Such a source can be an alkali metal or silver salt of the monoanion.

[0656] It is preferred that the alkali metal cation is sodium orpotassium. It is preferred that the monoanion is SbF₆ ⁻, BAF, PF₆ ⁻, orBF₄ ⁻, and more preferred that it is BAF. It is preferred that T¹ ismethyl and/or S is chlorine. All other preferred groups and conditionsfor these polymerizations are the same as for polymerizations with (II).

[0657] In all of the above polymerizations, and the catalysts for makingthem it is preferred that R² and R⁵, if present, are2,6-diisopropylphenyl and R³ and R⁴ are hydrogen or methyl. Whencyclopentene is polymerized, is preferred that R² and R⁵ (if present)are 2,6-dimethylphenyl or 2,4,6-trimethylphenyl and that R³ and R⁴ takentogether are An. R², R³, R⁴ and R⁵ and other groups herein may also besubstituted hydrocarbyl. As previously defined, the substituent groupsin substituted hydrocarbyl groups (there may be one or more substituentgroups) should not substantially interfere with the polymerization orother reactions that the compound is undergoing. Whether a particulargroup will interfere can first be judged from the artisans generalknowledge and the particular polymerization or other reaction that isinvolved. For instance, in polymerizations where an alkyl aluminumcompound is used may not be compatible with the presence of groupscontaining an active (relatively acidic) hydrogen atom, such as hydroxylor carboxyl because of the known reaction of alkyl aluminum compoundswith such active hydrogen containing groups (but such polymerizationsmay be possible if enough “extra” alkyl aluminum compound is added toreact with these groups). However, in very similar polymerizations wherealkyl aluminum compounds are not present, these groups containing activehydrogen may be present. Indeed many of the polymerization processesdescribed herein are remarkably tolerant to the presence of variousfunctional groups. Probably the most important considerations as to theoperability of compounds containing any particular functional group arethe effect of the group on the coordination of the metal atom (ifpresent), and side reaction of the group with other process ingredients(such as noted above). Therefore of course, the further away from themetal atom the functional group is, the less likely it is to influence,say, a polymerization. If there is doubt as to whether a particularfunctional group, in a particular position, will affect a reaction,simple minimal experimentation will provide the requisite answer.Functional groups which may be present in R², R³, R⁴, R⁵, and othersimilar radicals herein include hydroxy, halo (fluoro, chloro, bromo andiodo), ether, ester, dialkylamino, carboxy, oxo (keto and aldehyo),nitro, amide, thioether, and imino. Preferred functional groups arehydroxy, halo, ether and dialkylamino.

[0658] Also in all of the polymerizations, the (cyclo)olefin may besubstituted hydrocarbyl. Suitable substituents include ether, keto,aldehyde, ester, carboxylic acid.

[0659] In all of the above polymerizations, with the exceptions notedbelow, the following monomer(s), to produce the corresponding homo- orcopolymers, are preferred to be used: ethylene; propylene; ethylene andpropylene; ethylene and an α-olefin; an α-olefin; ethylene and an alkylacrylate, especially methyl acrylate; ethylene and acrylic acid;ethylene and carbon monoxide; ethylene, and carbon monoxide and anacrylate ester or acrylic acid, especially methyl acrylate; propyleneand alkyl acrylate, especially methyl acrylate; cyclopentene;cyclopentene and ethylene; cyclopentene and propylene. Monomers whichcontain a carbonyl group, including esters, carboxylic acids, carbonmonoxide, vinyl ketones, etc., can be polymerized with Pd(II) containingcatalysts herein, with the exception of those-that require the presenceof a neutral or cationic Lewis acid or cationic Bronsted acid, which isusually called the “first compound” in claims describing suchpolymerization processes.

[0660] Another useful “monomer” for these polymerization processes is aC₄ refinery catalytic cracker stream, which will often contain a mixtureof n-butane, isobutane, isobutene, 1-butene, 2-butenes and small amountsof butadiene. This type of stream is referred to herein as a “crudebutenes stream”. This stream may act as both the monomer source and“solvent” for the polymerization. It is preferred that the concentrationof 1- and 2-butenes in the stream be as high as possible, since theseare the preferred compounds to be polymerized. The butadiene contentshould be minimized because it may be a polymerization catalyst poison.The isobutene may have been previously removed for other uses. Afterbeing used in the polymerization (during which much or most of the1-butene would have been polymerized), the butenes stream can bereturned to the refinery for further processing.

[0661] In many of the these polymerizations certain general trends maybe noted, although for all of these trends there are exceptions. Thesetrends (and exceptions) can be gleaned from the Examples.

[0662] Pressure of the monomers (especially gaseous monomers such asethylene) has an effect on the polymerizations in many instances. Higherpressure often affects the polymer microstructure by reducing branching,especially in ethylene containing polymers. This effect is morepronounced for Ni catalysts than Pd catalysts. Under certain conditionshigher pressures also seem to give higher productivities and highermolecular weight. When an acrylate is present and a Pd catalyst is used,increasing pressure seems to decrease the acrylate content in theresulting copolymer.

[0663] Temperature also affects these polymerizations. Highertemperature usually increases branching with Ni catalysts, but often haslittle such effect using Pd catalysts. With Ni catalysts, highertemperatures appear to often decrease molecular weight. With Pdcatalysts, when acrylates are present, increasing temperature usuallyincreases the acrylate content of the polymer, but also often decreasesthe productivity and molecular weight of the polymer.

[0664] Anions surprisingly also often affect molecular weight of thepolymer formed. More highly coordinating anions often give lowermolecular weight polymers. Although all of the anions useful herein arerelatively weakly coordinating, some are more strongly coordinating thanothers. The coordinating ability of such anions is known and has beendiscussed in the literature, see for instance W. Beck., et al., Chem.Rev., vol. 88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol.93, p. 927-942 (1993), both of which are hereby included by reference.The results found herein in which the molecular weight of the polymerproduced is related to the coordinating ability of the anion used, is inline with the coordinating abilities of these anions as described inBeck (p. 1411) and Strauss (p. 932, Table II).

[0665] In addition to the “traditional” weakly coordinating anions citedin the paragraph immediately above, heterogeneous anions may also beemployed. In these cases, the true nature of the counterion is poorlydefined or unknown. Included in this group are MAO, MMAO and relatedaluminoxanes which do not form true solutions. The resulting counterionsare thought to bear anionic aluminate moieties related to those cited inthe paragraph immediately above. Polymeric anionic materials such asNafion″ polyfluorosulfonic acid can function as non-coordinatingcounterions. In addition, a wide variety of heterogeneous inorganicmaterials can be made to function as non-coordinating counterions.Examples would include aluminas, silicas, silica/aluminas, cordierites,clays, MgCl₂, and many others utilized as traditional supports forZiegler-Natta olefin polymerization catalysts. These are generallymaterials which have Lewis or Bronsted acidity. High surface area isusually desired and often these materials will have been activatedthrough some heating process. Heating may remove excess surface waterand change the surface acidity from Bronsted to Lewis type. Materialswhich are not active in the role may often be made active by surfacetreatment. For instance, a surface-hydrated silica, zinc oxide or carboncan be treated with an organoaluminum compound to provide the requiredfunctionality.

[0666] The catalysts described herein can be heterogenized through avariety of means. The heterogeneous anions in the paragraph immediatelyabove will all serve to heterogenize the catalysts. Catalysts can alsobe heterogenized by exposing them to small quantities of a monomer toencapsulate them in a polymeric material through which additionalmonomers will diffuse. Another method is to spray-dry the catalyst withits suitable non-coordinating counterion onto a polymeric support.Heterogeneous versions of the catalyst are particularly useful forrunning gas-phase polymerizations. The catalyst is suitably diluted anddispersed on the surface of the catalyst support to control the heat ofpolymerization. When applied to fluidized-bed polymerizations, theheterogeneous supports provide a convenient means of catalystintroduction.

[0667] Anions have been found to have another unexpected effect. Theycan effect the amount of incorporation of an acrylic monomer such as anester into an olefin/acrylic copolymer. For instance it has been foundthat SbF₆ ⁻ anion incorporates more fluorinated alkyl acrylate esterinto an ethylene copolymer than BAF anion, see for instance Example 302.

[0668] Another item may effect the incorporation of polar monomers suchas acrylic esters in olefin copolymers. It has been found that catalystscontaining less bulky α-diimines incorporate more of the polar monomerinto the polymer (one obtains a polymer with a higher percentage ofpolar monomer) than a catalyst containing a more bulky α-diimine,particularly when ethylene is the olefin comonomer. For instance, in anα-diimine of formula (VIII), if R² and R⁵ are 2,6-dimethylphenyl insteadof 2,6-diisopropylphenyl, more acrylic monomer will be incorporated intothe polymer. However, another common effect of using a less bulkycatalyst is to produce a polymer with lower molecular weight. Thereforeone may have to make a compromise between polar monomer content in thepolymer and polymer molecular weight.

[0669] When an olefinic carboxylic acid is polymerized into the polymer,the polymer will of course contain carboxyl groups. Similarly in anester containing polymer, some or all of the ester groups may behydrolyzed to carboxyl groups (and vice versa). The carboxyl groups maybe partially or completely converted into salts such as metallic salts.Such polymeric salts are termed ionomers. Ionomers are useful inadhesives, as ionomeric elastomers, and as molding resins. Salts may bemade with ions of metals such as Na, K, Zn, Mg, Al, etc. The polymericsalts may be made by methods known to the artisan, for instance reactionof the carboxylic acid containing polymers with various compounds of themetals such as bases (hydroxides, carbonates, etc.) or other compounds,such as acetylacetonates. Novel polymers that contain carboxylic acidgroups herein, also form novel ionomers when the carboxylic acid groupsare partially or fully converted to carboxylate salts.

[0670] When copolymers of an olefinic carboxylic acid or olefinic esterand selected olefins are made, they may be crosslinked by variousmethods known in the art, depending on the specific monomers used tomake the polymer. For instance, carboxyl or ester containing polymersmay be crosslinked by reaction with diamines to form bisamides. Certainfunctional groups which may be present on the polymer may be induced toreact to crosslink the polymer. For instance epoxy groups (which may bepresent as glycidyl esters) may be crosslinked by reaction of the epoxygroups, see for instance Example 135.

[0671] It has also been found that certain fluorinated olefins, some ofthem containing other functional groups may be polymerized by nickel andpalladium catalysts. Note that these fluorinated olefins are includedwithin the definition of H₂C═CHR¹⁷, wherein R¹⁷ can be considered to besubstituted hydrocarbyl, the substitution being fluorine and possiblyother substituents. Olefins which may be polymerized includeH₂C═CH(CH₂)_(a)R_(f)R⁴² wherein a is an integer of 2 to 20, R_(f) isperfluoroalkylene optionally containing one or more ether groups, andR⁴² is fluorine or a functional group. Suitable functional groupsinclude hydrogen, chlorine, bromine or iodine, ester, sulfonic acid(—SO₃H), and sulfonyl halide. Preferred groups for R⁴² include fluorine,ester, sulfonic acid, and sulfonyl fluoride. A sulfonic acid groupcontaining monomer does not have to be polymerized directly. It ispreferably made by hydrolysis of a sulfonyl halide group already presentin an already made polymer. It is preferred that the perfluoroalkylenegroup contain 2 to 20 carbon atoms and preferred perfluoroalkylenegroups are —(CF₂)_(b)— wherein b is 2 to 20, and (—CF₂)_(d)OCF₂CF₂—wherein d is 2 to 20. A preferred olefinic comonomer is ethylene or alinear α-olefin, and ethylene is especially preferred. Polymerizationsmay be carried out with many of the catalysts described herein, seeExamples 284 to 293.

[0672] As described herein, the resulting fluorinated polymers oftendon't contain the expected amount of branching, and/or the lengths ofthe branches present are not those expected for a simple vinylpolymerization.

[0673] The resulting polymers may be useful for compatibilizingfluorinated and nonfluorinated polymers, for changing the surfacecharacteristics of fluorinated or nonfluorinated polymers (by beingmixed with them), as molding resins, etc. Those polymers containingfunctional groups may be useful where those functional groups may reactor be catalysts. For instance, if a polymer is made with a sulfonylfluoride group (R⁴² is sulfonyl fluoride) that group may be hydrolyzedto a sulfonic acid, which being highly fluorinated is well known to be avery strong acid. Thus the polymer may be used as an acid catalyst, forexample for the polymerization of cyclic ethers such as tetrahydrofuran.

[0674] In this use it has been found that this polymer is more effectivethan a completely fluorinated sulfonic acid containing polymer. For suchuses the sulfonic acid content need not be high, say only 1 to 20 molepercent, preferably about 2 to 10 mole percent of the repeat units inthe polymer having sulfonic acid groups. The polymer may be crosslinked,in which case it may be soluble in the medium (for instancetetrahydrofuran), or it may be crosslinked so it swollen but notdissolved by the medium, Or it may be coated onto a substrate andoptionally chemically attached and/or crosslinked, so it may easily beseparated from the other process ingredients.

[0675] One of the monomers that may be polymerized by the abovecatalysts is ethylene (E), either by itself to form a homopolymer, orwith α-olefins and/or olefinic esters or carboxylic acids. The structureof the polymer may be unique in terms of several measurable properties.

[0676] These polymers, and others herein, can have unique structures interms of the branching in the polymer. Branching may be determined byNMR spectroscopy (see the Examples for details), and this analysis candetermine the total number of branches, and to some extent the length ofthe branches. Herein the amount of branching is expressed as the numberof branches per 1000 of the total methylene (—CH₂—) groups in thepolymer, with one exception. Methylene groups that are in an estergrouping, i.e. —CO₂ R, are not counted as part of the 1000 methylenes.These methylene groups include those in the main chain and in thebranches. These polymers, which are E homopolymers, have a branchcontent of about 80 to about 150 branches per 1000 methylene groups,preferably about 100 to about 130 branches per 1000 methylene groups.These branches do not include polymer end groups. In addition thedistribution of the sizes (lengths) of the branches is unique. Of theabove total branches, for every 100 that are methyl, about 30 to about90 are ethyl, about 4 to about 20 are propyl, about 15 to about 50butyl, about 3 to about 15 are amyl, and about 30 to about 140 are hexylor longer, and it is preferred that for every 100 that are methyl, about50 to about 75 are ethyl, about 5 to about 15 are propyl, about 24 toabout 40 are butyl, about 5 to 10 are amyl, and about 65 to about 120are hexyl or larger. These E homopolymers are often amorphous, althoughin some there may be a small amount of crystallinity.

[0677] Another polyolefin, which is an E homopolymer that can be made bythese catalysts has about 20 to about 150 branches per 1000 methylenegroups, and, per 100 methyl groups, about 4 to about 20 ethyl groups,about 1 to about 12 propyl groups, about 1 to about 12 butyl group,about 1 to about 10 amyl groups, and 0 to about 20 hexyl or largergroups. Preferably this polymer has about 40 to about 100 methyl groupsper 1000 methylene. groups, and per 100 methyl groups, about 6 to about15 ethyl groups, about 2 to about 10 propyl groups, about 2 to about 10butyl groups, about 2 to about 8 amyl groups, and about 2 to about 15hexyl or larger groups.

[0678] Many of the polyolefins herein, including homopolyethylenes, maybe crosslinked by various methods known in the art, for instance by theuse of peroxide or other radical generating species which can crosslinkthese polymers. Such crosslinked polymers are novel when theuncrosslinked polymers from which they are derived are novel, becausefor the most part the structural feature(s) of the uncrosslinkedpolymers which make them novel will be carried over into the crosslinkedforms.

[0679] In addition, some of the E homopolymers have an exceptionally lowdensity, less than about 0.86 g/mL, preferably about 0.85 g/mL or less,measured at 25° C. This density is based on solid polymer.

[0680] Homopolymers of polypropylene (P) can also have unusualstructures. Similar effects have been observed with other α-olefins(e.g. 1-hexene). A “normal” P homopolymer will have one methyl group foreach methylene group (or 1000 methyl groups per 1000 methylene groups),since the normal repeat unit is —CH(CH₃)CH₂—. However, using a catalystof formula (I) in which M is Ni(II) in combination with an alkylaluminum compound it is possible to produce a P homopolymer with about400 to about 600 methyl groups per 1000 methylene groups, preferablyabout 450 to about 550 methyl groups per 1000 methylene groups. Similareffects have been observed with other α-olefins (e.g. 1-hexene).

[0681] In the polymerization processes described herein olefinic estersand/or carboxylic acids may also be present, and of course become partof the copolymer formed. These esters may be copolymerized with one ormore of E and one or more α-olefins. When copolymerized with E alonepolymers with unique structures may be formed.

[0682] In many such E/olefinic ester and/or carboxylic acid copolymersthe overall branching level and the distribution of branches of varioussizes are unusual. In addition, where and how the esters or carboxylicacids occur in the polymer is also unusual. A relatively high proportionof the repeat units derived from the olefinic esters are at the ends ofbranches. In such copolymers, it is preferred that the repeat unitsderived from the olefinic esters and carboxylic acids are about 0.1 to40 mole percent of the total repeat units, more preferably about 1 toabout 20 mole percent. In a preferred ester, m is 0 and R¹ ishydrocarbyl or substituted hydrocarbyl. It is preferred that R¹ is alkylcontaining 1 to 20 carbon atoms, more preferred that it contains 1 to 4carbon atoms, and especially preferred that R¹ is methyl.

[0683] One such preferred dipolymer has about 60 to 100 methyl groups(excluding methyl groups which are esters) per 1000 methylene groups inthe polymer, and contains, per 100 methyl branches, about 45 to about 65ethyl branches, about 1 to about,3 propyl branches, about 3 to about 10butyl branches, about 1 to about 3 amyl branches, and about 15 to about25 hexyl or longer branches. In addition, the ester and carboxylic acidcontaining repeat units are often distributed mostly at the ends of thebranches as follows. If the branches, and the carbon atom to which theyare attached to the main chain, are of the formula —CH(CH₂)_(n)CO₂R¹,wherein the CH is part of the main chain, then in some of these polymersabout 40 to about 50 mole percent of ester groups are found in brancheswhere n is 5 or more, about 10 to about 20 mole percent when n is 4,about 20 to 30 mole percent when n is 1, 2 and 3 and about 5 to about 15mole percent when n is 0. When n is 0, an acrylate ester has polymerized“normally” as part of the main chain, with the repeat unit—CH₂—CHCO₂R¹—.

[0684] These branched polymers which contain olefin and olefinic estermonomer units, particularly copolymers of ethylene and methyl acrylateand/or other acrylic esters are particularly useful as viscositymodifiers for lubricating oils, particularly automotive lubricatingoils.

[0685] Under certain polymerization conditions, some of thepolymerization catalysts described herein produce polymers whosestructure is unusual, especially considering from what compounds(monomers) the polymers were made, and the fact that polymerizationcatalysts used herein are so-called transition metal coordinationcatalysts (more than one compound may be involved in the catalystsystem, one of which must include a transition metal). Some of thesepolymers were the number of theoretical branches in a polymer made from50 mole percent ethylene (e=0), 30 mole percent propylene (e=1) and 20mole percent methyl 5-heptenoate (e=4) would be as follows:${{Theoretical}\quad {branches}} = {\frac{1000 \circ 0.5}{\{ {\lbrack ( {2 \circ 0.5} ) \rbrack + \lbrack {( {0.30 \circ 1} ) + ( {0.20 \circ 4} )} \rbrack} \}} = {238\quad {( {{{branches}/1000}\quad {methylenes}} ).}}}$

[0686] The “1000 methylenes” include all of the methylene groups in thepolymer, including methylene groups in the branches.

[0687] For some of the polymerizations described herein, the actualamount of branching present in the polymer is considerably greater thanor less than the above theoretical branching calculations wouldindicate. For instance, when an ethylene homopolymer is made, thereshould be no branches, yet there are often many such branches. When anα-olefin is polymerized, the branching level may be much lower or higherthan the theoretical branching level. It is preferred that the actualbranching level is at 90% or less of the theoretical branching level,more preferably about 80% or less of the theoretical branching level, or110% or more of the theoretical branching level, more preferably about120% or more of the theoretical branching level. The polymer should alsohave at least about 50 branches per 1000 methylene units, preferablyabout 75 branches per 1000 methylene units, and more preferably about100 branches per 1000 methylene units. In cases where there are “0”branches theoretically present, as in ethylene homopolymers orcopolymers with acrylics, excess branches as a percentage cannot becalculated. In that instance if the polymer has 50 or more, preferably75 or more branches per 1000 methylene groups, it has excess branches(i.e. in branches in which f>0).

[0688] These polymers also have “at least two branches of differentlengths containing less than 6 carbon atoms each.” By this is meant thatbranches of at least two different lengths (i.e. number of carbonatoms), and containing less than 6 carbon atoms, are present in thepolymer. For instance the polymer may contain ethyl and butyl branches,or methyl and amyl branches.

[0689] As will be understood from the above discussion, the lengths ofthe branches (“f”) do not necessarily correspond to the original sizesof the monomers used (“e”). Indeed branch lengths are often presentwhich do not correspond to the sizes of any of the monomers used and/ora branch length may be present “in excess”. By “in excess” is meantthere are more branches of a particular length present than there weremonomers which corresponded to that branch length in the polymer. Forinstance, in the copolymerization of 75 mole percent ethylene and 25mole percent 1-butene it would be expected that there would be 125 ethylbranches per 1000 methylene carbon atoms. If there were more ethylbranches than that, they would be in excess compared to the theoreticalbranching. There may also be a deficit of specific length branches. Ifthere were less than 125 ethyl branches per 1000 methylene groups inthis polymer there would be a deficit. Preferred polymers have 90% orless or 110% or more of the theoretical amount of any branch lengthpresent in the polymer, and it is especially preferred if these branchesare about 80% or less or about 120% or more of the theoretical amount ofany branch length. In the case of the 75 mole percent ethylene/25 molepercent 1-butene polymer, the 90% would be about 113 ethyl branches orless, while the 110% would be about 138 ethyl branches or more. Suchpolymers may also or exclusively contain at least 50 branches per 1000methylene atoms with lengths which should not theoretically (asdescribed above) be present at all.

[0690] These polymers also have “at least two branches of differentlengths containing less than 6 carbon atoms each.” By this is meant thatbranches of at least two different lengths (i.e. number of carbonatoms), and containing less than 6 carbon atoms, are present in thepolymer. For instance the polymer may contain ethyl and butyl branches,or methyl and amyl branches.

[0691] Some of the polymers produced herein are novel because of unusualstructural features. Normally, in polymers of alpha-olefins of theformula CH₂═CH(CH₂)_(a)H wherein a is an integer of 2 or more made bycoordination polymerization, the most abundant, and often the only,branches present in such polymers have the structure —(CH₂)_(a)H. Someof the polymers produced herein are novel because methyl branchescomprise about 25% to about 75% of the total branches in the polymer.Such polymers are described in Examples 139, 162, 173 and 243-245. Someof the polymers produced herein are novel because in addition to havinga high percentage (25-75%) of methyl branches (of the total branchespresent), they also contain linear branches of the structure —(CH₂)_(n)Hwherein n is an integer of six or greater. Such polymers are describedin Examples 139, 173 and 243-245. Some of the polymers produced hereinare novel because in addition to having a high percentage (25-75%) ofmethyl branches (of the total branches present), they also contain thestructure (XXVI), preferably in amounts greater than can be accountedfor by end groups, and more preferably greater than 0.5 (XXVI) groupsper thousand methyl groups in the polymer greater than can be accountedfor by end groups.

[0692] Normally, homo- and copolymers of one or more alpha-olefins ofthe formula CH₂═CH(CH₂)_(a)H wherein a is an integer of 2 or morecontain as part of the polymer backbone the structure (XXV)

[0693] wherein R³⁵ and R³⁶ are alkyl groups. In most such polymers ofalpha-olefins of this formula (especially those produced bycoordination-type polymerizations), both of R³⁵ and R³⁶ are —(CH₂)_(a)H.However, in certain of these polymers described herein, about 2 molepercent or more, preferably about 5 mole percent or more and morepreferably about 50 mole percent or more of the total amount of (XXV) insaid polymer consists of the structure where one of R³⁵ and R³⁶ is amethyl group and the other is an alkyl group containing two or morecarbon atoms. Furthermore, in certain of these polymers describedherein, structure (XXV) may occur in side chains as well as in thepolymer backbone. Structure (XXV) can be detected by ¹³C NMR. The signalfor the carbon atom of the methylene group between the two methinecarbons in (XXV) usually occurs in the ¹³C NMR at 41.9 to 44.0 ppm whenone of R³⁵ and R³⁶ is a methyl group and the other is an alkyl groupcontaining two or more carbon atoms, while when both R³⁵ and R³⁶ contain2 or more carbon atoms, the signal for the methylene carbon atom occursat 39.5 to 41.9 ppm. Integration provides the relative amounts of thesestructures present in the polymer. If there are interfering signals fromother carbon atoms in these regions, they must be subtracted from thetotal integrals to give correct values for structure (XXV).

[0694] Normally, homo- and copolymers of one or more alpha-olefins ofthe formula CH₂═CH(CH₂)_(a)H wherein a is an integer of 2 or more(especially those made by coordination polymerization) contain as partof the polymer backbone structure (XXIV) wherein n is 0, 1, or 2. When nis 0, this structure is termed “head to head” polymerization. When n is1, this structure is termed “head to tail” polymerization. When n is 2,this structure is termed “tail to tail” polymerization. In most suchpolymers of alpha-olefins of this formula (especially those produced bycoordination-type polymerizations), both of R³⁷ and R³⁸ are —(CH₂)_(a)H.However some of the polymers of alpha-olefins of this formula describedherein are novel in that they also contain structure (XXIV) wherein n=a,R³⁷ is a methyl group, and R³⁸ is an alkyl group with 2 or more carbonatoms.

[0695] Normally polyethylene made by coordination polymerization has alinear backbone with either no branching, or small amounts of linearbranches. Some of the polyethylenes described herein are unusual in thatthey contain structure (XXVII) which has a methine carbon that is notpart of the main polymer backbone.

[0696] Normally, polypropylene made by coordination polymerization hasmethyl branches and few if any branches of other sizes. Some of thepolypropylenes described herein are unusual in that they contain one orboth of the structures (XXVIII) and (XXIX).

[0697] As the artisan understands, in coordination polymerizationalpha-olefins of the formula CH₂═CH(CH₂)_(a)H may insert into thegrowing polymer chain in a 1,2 or 2,1 manner. Normally these insertionsteps lead to 1,2-enchainment or 2,1-enchainment of the monomer. Both ofthese fundamental steps form a —(CH₂)_(a)H branch. However, with somecatalysts herein, some of the initial product of 1,2 insertion canrearrange by migration of the coordinated metal atom to the end of thelast inserted monomer before insertion of additional monomer occurs.This results in omega,2-enchainment and the formation of a methylbranch.

[0698] It is also known that with certain other catalysts, some of theinitial product of 2,1 insertion can rearrange in a similar manner bymigration of the coordinated metal atom to the end of the last insertedmonomer. This results in omega,1-enchainment and no branch is formed.

[0699] Of the four types of alpha-olefin enchainment,omega,1-enchainment is unique in that it does not generate a branch. Ina polymer made from an alpha-olefin of the formula CH₂═CH(CH₂)_(a)H, thetotal number of branches per 1000 methylene groups (B) can be expressedas:

B=(1000)(1−X _(ω,1))/[(1−X _(ω,1))a+X _(ω,1)(a+2)]

[0700] where X_(ω,1) is the fraction of omega,1-enchainment Solving thisexpression for X_(ω,1) gives:

X _(ω,1)=(1000−aB)/(1000+2B)

[0701] This equation provides a means of calculating the fraction ofomega,1-enchainment in a polymer of a linear alpha-olefin from the totalbranching B. Total branching can be measured by ¹H NMR or ¹³C NMR.Similar equations can be written for branched alpha-olefins. Forexample, the equation for 4-methyl-1-pentene is:

X _(ω,1)=(2000−2B)/(1000+2B)

[0702] Most polymers of alpha-olefins made by other coordinationpolymerization methods have less than 5% omega,1-enchainment. Some ofthe alpha-olefin polymers described herein have unusually large amounts(say >5%) of omega,1-enchainment. In essence this is similar to statingthat a polymer made from an α-olefin has much less than the “expected”amount of branching. Although many of the polymerizations describedherein give substantial amounts of ω,1- and other unusual forms ofenchainment of olefinic monomers, it has surprisingly been found that“unsymmetrical” α-diimine ligands of formula (VIII) give especially highamounts of ω,1-enchainment. In particular when R² and R⁵ are phenyl, andone or both of these is substituted in such a way as different sizedgroups are present in the 2 and 6 position of the phenyl ring(s),ω,1-enchainment is enhanced. For instance, if one or both of R² and R⁵are 2-t-butylphenyl, this enchainment is enhanced. In this context whenR² and/or R⁵ are “substituted” phenyl the substitution may be not onlyin the 2 and/or 6 positions, but on any other position in the phenylring. For instance, 2,5-di-t-butylphenyl, and2-t-butyl-4,6-dichlorophenyl would be included in substituted phenyl.

[0703] The steric effect of various groupings has been quantified by aparameter called E_(s), see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74,p. 3120-3128, and M. S. Newman, Steric Effects in Organic Chemistry,John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein,the E_(s) values are those for o-substituted benzoates described inthese publications. If the value for E_(s) for any particular group isnot known, it can be determined by methods described in thesepublications. For the purposes herein, the value of hydrogen is definedto be the same as for methyl. It is preferred that difference in E_(s),when R² (and preferably also R⁵) is phenyl, between the groupssubstituted in the 2 and 6 positions of the phenyl ring is at least0.15, more preferably at least about 0.20, and especially preferablyabout 0.6 or more. These phenyl groups may be unsubstituted orsubstituted in any other manner in the 3, 4 or 5 positions.

[0704] These differences in E_(s) are preferred in a diimine such as(VIII), and in any of the polymerization processes herein wherein ametal complex containing an α-diimine ligand is used or formed. Thesynthesis and use of such α-diimines is illustrated in Examples 454-463.

[0705] Because of the relatively large amounts of ω,1-enchainment thatmay be obtained using some of the polymerization catalysts reportedherein novel polymers can be made. Among these homopolypropylene (PP).In some of the PP's made herein the structure

[0706] may be found. In this structure each C^(a) is a methine carbonatom that is a branch point, while each C^(b) is a methylene group thatis more than 3 carbon atoms removed from any branch point (C^(a)).Herein methylene groups of the type —C^(b)H₂— are termed δ+ (or delta+)methylene groups. Methylene groups of the type —C^(d)H₂— which areexactly the third carbon atom from a branch point, are termed γ (gamma)methylene groups. The NMR signal for the δ+ methylene groups occurs atabout 29.75 ppm, while the NMR signal for the γ methylene groups appearsat about 30.15 ppm. Ratios of these types of methylene groups to eachother and the total number of methylene groups in the PP is done by theusual NMR integration techniques.

[0707] It is preferred that PP's made herein have about 25 to about 300δ+ methylene groups per 1000 methylene groups (total) in the PP.

[0708] It is also preferred that the ratio of δ+:γ methylene groups inthe PP be 0.7 to about 2.0.

[0709] The above ratios involving δ+ and γ methylene groups in PP are ofcourse due to the fact that high relatively high ω,1 enchainment can beobtained. It is preferred that about 30 to 60 mole percent of themonomer units in PP be enchained in an ω,1 fashion. Using the aboveequation, the percent ω,1 enchainment for polypropylene can becalculated as:

% ω,1=(100)(1000−B)/(1000+2B)

[0710] wherein B is the total branching (number of methyl groups) per1000 methylene groups in the polymer.

[0711] Homo- or copolymers of one or more linear α-olefins containing 3to 8 carbon atoms may also have δ+ carbon atoms in them, preferably atleast about 1 or more δ+ carbon atoms per 1000 methylene groups.

[0712] The above polymerization processes can of course be used to makerelatively random copolymers (except for certain CO copolymers) ofvarious possible monomers. However, some of them can also be used tomake block polymers. A block polymer is conventionally defined as apolymer comprising molecules in which there is a linear arrangement ofblocks, a block being a portion of a polymer molecule which themonomeric units have at least one constitutional or configurationalfeature absent from adjacent portions (definition from H. Mark, et al.,Ed., Encyclopedia of Polymer Science and Engineering, Vol. 2, John Wiley& Sons, New York, 1985, p. 324). Herein in a block copolymer, theconstitutional difference is a difference in monomer units used to makethat block, while in a block homopolymer the same monomer(s) are usedbut the repeat units making up different blocks are different structureand/or ratios of types of structures.

[0713] Since it is believed that many of the polymerization processesherein have characteristics that often resemble those of livingpolymerizations, making block polymers may be relatively easy. Onemethod is to simply allow monomer(s) that are being polymerized to bedepleted to a low level, and then adding different monomer(s) or thesame combination of monomers in different ratios. This process may berepeated to obtain polymers with many blocks.

[0714] Lower temperatures, say about less than 0° C., preferably about−10° to about −30°, tends to enhance the livingness of thepolymerizations. Under these conditions narrow molecular weightdistribution polymers may be obtained (see Examples 367-369 and 371),and block copolymers may also be made (Example 370).

[0715] As pointed out above, certain polymerization conditions, such aspressure, affect the microstructure of many polymers. The microstructurein turn affects many polymer properties, such as crystallization. Thus,by changing polymerization conditions, such as the pressure, one canchange the microstructure of the part of the polymer made under thoseconditions. This of course leads to a block polymer, a polymer havedefined portions having structures different from other definedportions. This may be done with more than one monomer to obtain a blockcopolymer, or may be done with a single monomer or single mixture ofmonomers to obtain a block homopolymer. For instance, in thepolymerization of ethylene, high pressure sometimes leads to crystallinepolymers, while lower pressures give amorphous polymers. Changing thepressure repeatedly could lead to an ethylene homopolymer containingblocks of amorphous polyethylene and blocks of crystalline polyethylene.If the blocks were of the correct size, and there were enough of them, athermoplastic elastomeric homopolyethylene could be produced. Similarpolymers could possibly be made from other monomer(s), such aspropylene.

[0716] Homopolymers of α-olefins such as propylene, that is polymerswhich were made from a monomer that consisted essentially of a singlemonomer such as propylene, which are made herein, sometimes exhibitunusual properties compared to their “normal” homopolymers. Forinstance, such a homopolypropylene usually would have about 1000 methylgroups per 1000 methylene groups. Polypropylenes made herein typicallyhave about half that many methyl groups, and in addition have somelonger chain branches. Other α-olefins often give polymers whosemicrostructure is analogous to these polypropylenes when the abovecatalysts are used for the polymerization.

[0717] These polypropylenes often exhibit exceptionally low glasstransition temperatures (Tg's). “Normal” polypropylene has a Tg of about−17° C., but the polypropylenes herein have a Tg of −30° C. or less,preferably about −35° C. or less, and more preferably about −40° C. orless. These Tg's are measured by Differential Scanning Calorimetry at aheating rate of 10° C./min, and the Tg is taken as the midpoint of thetransition. These polypropylenes preferably have at least 50 branches(methyl groups) per 1000 carbon atoms, more preferably at least about100 branches per 1000 methylene groups.

[0718] Previously, when cyclopentene was coordination polymerized tohigher molecular weights, the resulting polymer was essentiallyintractable because of its very high melting point, greatly above 300°C. Using the catalysts here to homopolymerize cyclopentene results in apolymer that is tractable, i.e., may be reformed, as by melt forming.Such polymers have an end of melting point of about 320° C. or less,preferably about 300° C. or less, or a melting point of about 275° C. orless, preferably about 250° C. or less. The melting point is determinedby Differential Scanning Calorimetry at a heating rate of 15° C./min,and taking the maximum of the melting endotherm as the melting point.However these polymers tend to have relatively diffuse melting points,so it is preferred to measure the “melting point” by the end of meltingpoint. The method is the same, except the end of melting is taken as theend (high temperature end) of the melting endotherm which is taken asthe point at which the DSC signal returns to the original (extrapolated)baseline. Such polymers have an average degree of polymerization(average number of cyclopentene repeat units per polymer chain) of about10 or more, preferably about 30 or more, and more preferably about 50 ormore.

[0719] In these polymers, enchainment of the cyclopentene repeat unitsis usually as cis-1,3-pentylene units, in contrast to many prior artcyclopentenes which were enchained as 1,2-cyclopentylene units. It ispreferred that about 90 mole percent or more, more preferably about 95mole percent or more of the enchained cyclopentene units be enchained as1,3-cyclopentylene units, which are preferably cis-1,3-cyclopentyleneunits.

[0720] The X-ray powder diffraction pattern of the instantpoly(cyclopentenes) is also unique. To produce cyclopentene polymersamples of uniform thickness for X-ray measurements, powder samples werecompressed into disks approximately 1 mm thick and 32 mm in diameter.X-ray powder diffraction patterns of the samples were collected over therange 10-50° 2θ. The diffraction data were collected using an automatedPhilips θ-θ diffractometer (Philips X'pert System) operating in thesymmetrical transmission mode (Ni-filtered CuKa radiation, equipped witha diffracted beam collimator (Philips Thin Film Collimator system), Xefilled proportional detector, fixed step mode (0.05°/step), 12.5sec./step, 1/4° divergence slit). Reflection positions were identifiedusing the peak finding routine in the APD suite of programs providedwith the X'pert System. The X-ray powder diffraction pattern hadreflections at approximately 17.3°, 19.3°, 24.2°, and 40.70° 2θ, whichcorrespond to d-spacings of approximately 0.512, 0.460, 0.368 and 0.222nm, respectively. These polymers have a monoclinic unit cell of theapproximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and g=123.2°.

[0721] Copolymers of cyclopentene and various other olefins may also bemade. For instance a copolymer of ethylene and cyclopentene may also bemade. In such a copolymer it is preferred that at least 50 mole percent,more preferably at least about 70 mole percent, of the repeat units arederived from cyclopentene. As also noted above, many of thepolymerization systems described herein produce polyethylenes that haveconsiderable branching in them. Likewise the ethylene units which arecopolymerized with the cyclopentene herein may also be branched, so itis preferred that there be at least 20 branches per 1000 methylenecarbon atoms in such copolymers. In this instance, the “methylene carbonatoms” referred to in the previous sentence do not include methylenegroups in the cyclopentene rings. Rather it includes methylene groupsonly derived from ethylene or other olefin, but not cyclopentene.

[0722] Another copolymer that may be prepared is one from cyclopenteneand an α-olefin, more preferably a linear α-olefin. It is preferred insuch copolymers that repeat units derived from cyclopentene are 50 molepercent or more of the repeat units. As mentioned above, α-olefins maybe enchained in a 1,ω fashion, and it is preferred that at least 10 molepercent of the repeat units derived from the α-olefin be enchained insuch a fashion. Ethylene may also be copolymerized with the cyclopenteneand α-olefin.

[0723] Poly(cyclopentene) and copolymers of cyclopentene, especiallythose that are (semi)crystalline, may be used as molding and extrusionresins. They may contain various materials normally found in resins,such as fillers, reinforcing agents, antioxidants, antiozonants,pigments, tougheners, compatibilizers, dyes, flame retardant, and thelike. These polymers may also be drawn or melt spun into fibers.Suitable tougheners and compatibilizers include polycyclopentene resinwhich has been grafted with maleic anhydride, an grafted EPDM rubber, agrafted EP rubber, a functionalized styrene/butadiene rubbers or otherrubber which has been modified to selectively bond to components of thetwo phases.

[0724] In all of the above homo- and copolymers of cyclopentene, whereappropriate, any of the preferred state may be combined any otherpreferred state(s).

[0725] The homo- and copolymers of cyclopentene described above may usedor made into certain forms as described below:

[0726] 1. The cyclopentene polymers described above may be part of apolymer blend. That is they may be mixed in any proportion with one ormore other polymers which may be thermoplastics and/or elastomers.Suitable polymers for blends are listed below in the listing for blendsof other polymers described herein. One preferred type of polymer whichmay be blended is a toughening agent or compatibilizer, which is oftenelastomeric and/or contains functional groups which may helpcompatibilize the mixture, such as epoxy or carboxyl.

[0727] 2. The polycyclopentenes described herein are useful in anonwoven fabric comprising fibrillated three-dimensional network fibersprepared by using of a polycyclopentene resin as the principalcomponent. It can be made by flash-spinning a homogeneous solutioncontaining a polycyclopentene. The resultant nonwoven fabric isexcellent in heat resistance, dimensional stability and solventresistance.

[0728] 3. A shaped part of any of the cyclopentene containing resins.This part may be formed by injection molding, extrusion, andthermoforming. Exemplary uses include molded part for automotive use,medical treatment container, microwave-range container, food packagecontainer such as hot packing container, oven container, retortcontainer, etc., and heatresisting transparent container such asheat-resisting bottle.

[0729] 4. A sheet or film of any of the cyclopentene containing resins.This sheet or film may be clear and may be used for optical purposes(i.e. breakage resistant glazing). The sheet or film may be oriented orunoriented. Orientation may be carried out by any of the known methodssuch a uniaxial or biaxial drawing. The sheet or film may be stampableor thermoformable.

[0730] 5. The polycyclopentene resins are useful in nonwoven fabrics ormicrofibers which are produced by melt-blowing a material containing asa main component a polycyclopentene. A melt-blowing process forproducing a fabric or fiber comprises supplying a polycyclopentene in amolten form from at least one orifice of a nozzle into a gas streamwhich attenuates the molten polymer into microfibers. The nonwovenfabrics are excellent in heat-resistant and chemical resistantcharacteristics, and are suitable for use as medical fabrics, industrialfilters, battery separators and so forth. The microfibers areparticularly useful in the field of high temperature filtration,coalescing and insulation.

[0731] 6. A laminate in which one or more of the layers comprises acyclopentene resin. The laminate may also contain adhesives, and otherpolymers in some or all of the layers, or other materials such as paper,metal foil, etc. Some or all of the layers, may be oriented in the sameor different directions. The laminate as a whole may also be oriented.Such materials are useful for containers, or other uses where barrierproperties are required.

[0732] 7. A fiber of a cyclopentene polymer. This fiber may be undrawnor drawn to further orient it. It is useful for apparel and inindustrial application where heat resistance and/or chemical resistanceare important.

[0733] 8. A foam or foamed object of a cyclopentene polymer. The foammay be formed in any conventional manner such as by using blowingagents.

[0734] 9. The cyclopentene resins may be microporous membranes. They maybe used in process wherein semi-permeable membranes are normally used.

[0735] In addition, the cyclopentene resins may be treated or mixed withother materials to improve certain properties, as follows:

[0736] 1. They may further be irradiated with electron rays. This oftenimproves heat resistance and/or chemical resistance, and is relativelyinexpensive. Thus the molding is useful as a material required to havehigh heat resistance, such as a structural material, a food containermaterial, a food wrapping material or an electric or electronic partmaterial, particularly as an electric or electronic part material,because it is excellent in soldering resistance.

[0737] 2. Parts with a crystallinity of at least 20% may be obtained bysubjecting cyclopentene polymers having an end of melting point between240 and 300° C. to heat treatment (annealing) at a temperature of 120°C. to just below the melting point of the polymer. Preferred conditionsare a temperature of 150 to 280° C. for a period of time of 20 secondsto 90 minutes, preferably to give a cyclopentene polymer which has aheat deformation temperature of from 200 to 260° C. These parts havegood physical properties such as heat resistance and chemicalresistance, and thus are useful for, for example, general constructionmaterials, electric or electronic devices, and car parts.

[0738] 3. Cyclopentene resins may be nucleated to promotecrystallization during processing. An example would be apolycyclopentene resin composition containing as main components (A) 100parts by weight of a polycyclopentene and (B) 0.01 to 25 parts by weightof one or more nucleating agents selected from the group consisting of(1) metal salts of organic acids, (2) inorganic compounds, (3)organophosphorus compounds, and/or (4) metal salts of ionic hydrocarboncopolymer. Suitable nucleating agents may be sodiummethylenebis(2,4-di-tertbutylphenyl) acid phosphate, sodiumbis(4-tert-butylphenyl) phosphate, aluminum p-(tert-butyl) benzoate,talc, mica, or related species. These could be used in a process forproducing polycyclopentene resin moldings by molding the abovepolycyclopentene resin composition at a temperature above their meltingpoint.

[0739] 4. Flame retardants and flame retardant combinations may be addedto a cyclopentene polymer. Suitable flame retardants include ahalogen-based or phosphorus-based flame retardant, antimony trioxide,antimony pentoxide, sodium antimonate, metallic antimony, antimonytrichloride, antimony pentachloride, antimony trisulfide, antimonypentasulfide, zinc borate, barium metaborate or zirconium oxide. Theymay be used in conventional amounts.

[0740] 5. Antioxidants may be used in conventional amounts to improvethe stability of the cyclopentene polymers. For instance 0.005 to 30parts by weight, per 100 parts by weight of the cyclopentene polymer, ofan antioxidant selected from the group consisting of a phosphorouscontaining antioxidant, a phenolic antioxidant or a combination thereof.The phosphorous containing antioxidant may be a monophosphite ordiphosphite or mixture thereof and the phenolic antioxidant may be adialkyl phenol, trialkyl phenol, diphenylmonoalkoxylphenol, a tetraalkylphenol, or a mixture thereof. A sulfur-containing antioxidant may alsobe used alone or in combination with other antioxidants.

[0741] 6. Various fillers or reinforcers, such as particulate or fibrousmaterials, may be added to improve various physical properties.

[0742] 7. “Special” physical properties can be obtained by the use ofspecific types of materials. Electrically conductive materials such asfine metallic wires or graphite may be used to render the polymerelectrically conductive. The temperature coefficient of expansion may beregulated by the use of appropriate fillers, and it may be possible toeven obtain materials with positive coefficients of expansion. Suchmaterials are particularly useful in electrical and electronic parts.

[0743] 8. The polymer may be crosslinked by irradiation or chemically asby using peroxides, optionally in the presence of suitable coagents.Suitable peroxides include benzoyl peroxide, lauroyl peroxide, dicumylperoxide, tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylcumylperoxide, tert-butylhydroperoxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,1-bis(tert-butylperoxyisopropyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tert-butylperoxy)valerate,2,2-bis(tert-butylperoxy)butane and tert-butylperoxybenzene.

[0744] When polymerizing cyclopentene, it has been found that some ofthe impurities that may be found in cyclopentene poison or otherwiseinterfere with the polymerizations described herein. Compounds such as1,3-pentadiene (which can be removed by passage through 5A molecularsieves), cyclopentadiene (which can be removed by distillation from Na),and methylenecyclobutane (which can be removed by distillation frompolyphosphoric acid), may interfere with the polymerization, and theirlevel should be kept as low as practically possible.

[0745] The above polymers (in general) are useful in many applications.Crystalline high molecular weight polymers are useful as molding resins,and for films for use in packaging. Amorphous resins are useful aselastomers, and may be crosslinked by known methods, such as by usingfree radicals. When such amorphous resins contain repeat units derivedfrom polar monomers they are oil resistant. Lower molecular weightpolymers are useful as oils, such as in polymer processing aids. Whenthey contain polar groups, particularly carboxyl groups, they are usefulin adhesives.

[0746] In many of the above polymerizations, the transition metalcompounds employed as (part of the) catalysts contain(s) (a) metalatom(s) in a positive oxidation state. In addition, these complexes mayhave a square planar configuration about the metal, and the metal,particularly nickel or palladium, may have a d⁸ electronicconfiguration. Thus some of these catalysts may be said to have a metalatom which is cationic and has a d⁸-square planar configuration.

[0747] In addition these catalysts may have a bidentate ligand whereincoordination to the transition metal is through two different nitrogenatoms or through a nitrogen atom and a phosphorus atom, these nitrogenand phosphorus atoms being part of the bidentate ligand. It is believedthat some of these compounds herein are effective polymerizationcatalysts at least partly because the bidentate ligands have sufficientsteric bulk on both sides of the coordination plane (of the squareplanar complex). Some of the Examples herein with the various catalystsof this type illustrate the degree of steric bulk which may be neededfor such catalysts. If such a complex contains a bidentate ligand whichhas the appropriate steric bulk, it is believed that it producespolyethylene with a degree of polymerization of at least about 10 ormore.

[0748] It is also believed that the polymerization catalysts herein areeffective because unpolymerized olefinic monomer can only slowlydisplace from the complex a coordinated olefin which may be formed byβ-hydride elimination from the growing polymer chain which is attachedto the transition metal. The displacement can occur by associativeexchange. Increasing the steric bulk of the ligand slows the rate ofassociative exchange and allows polymer chain growth. A quantitativemeasure of the steric bulk of the bidentate ligand can be obtained bymeasuring at −85° C. the rate of exchange of free ethylene withcomplexed ethylene in a complex of formula (XI) as shown in equation 1using standard ¹H NMR techniques, which is called herein the EthyleneExchange Rate (EER). The neutral bidentate ligand is represented by YNwhere Y is either N or P. The EER is measured in this system. In thismeasurement system the metal is always Pd, the results being applicableto other metals as noted below. Herein it is preferred for catalysts tocontain bidentate ligands for which the second order rate constant forEthylene Exchange Rate is about 20,000 L-mol-⁻¹s⁻¹ or less when themetal used in the polymerization catalyst is palladium, more preferablyabout 10,000 L-mol-⁻¹s⁻¹ or less, and more preferably about 5,000L-mol⁻¹s⁻¹ or less. When the metal in the polymerization catalyst isnickel, the second order rate constant (for the ligand in EERmeasurement) is about 50,000 L-mol⁻¹s⁻¹, more preferably about 25,000L-mol⁻¹s⁻¹ or less, and especially preferably about 10,000 L-mol⁻¹s⁻¹ orless. Herein the EER is measured using the compound (XI) in a procedure(including temperature) described in Examples 21-23.

[0749] In these polymerizations it is preferred if the bidentate ligandis an α-diimine. It is also preferred if the olefin has the formulaR¹⁷CH═CH₂, wherein R¹⁷ is hydrogen or n-alkyl.

[0750] In general for the polymers described herein, blends may beprepared with other polymers, and such other polymers may be elastomers,thermoplastics or thermosets. By elastomers are generally meant polymerswhose Tg (glass transition temperature) and Tm (melting point), ifpresent, are below ambient temperature, usually considered to be about20° C. Thermoplastics are those polymers whose Tg and/or Tm are at orabove ambient temperature. Blends can be made by any of the commontechniques known to the artisan, such as solution blending, or meltblending in a suitable apparatus such as a single or twin-screwextruder. Specific uses for the polymers of this application in theblends or as blends are listed below.

[0751] Blends may be made with almost any kind of elastomer, such as EP,EPDM, SBR, natural rubber, polyisoprene, polybutadiene, neoprene, butylrubber, styrene-butadiene block copolymers, segmentedpolyester-polyether copolymers, elastomeric polyurethanes, chlorinatedor chlorosulfonated polyethylene, (per)fluorinated elastomers such ascopolymers of vinylidene fluoride, hexafluoropropylene and optionallytetrafluoroethylene, copolymers of tetrafluoroethylene andperfluoro(methyl vinyl ether), and copolymers of tetrafluoroethylene andpropylene.

[0752] Suitable thermoplastics which are useful for blending with thepolymers described herein include: polyesters such as poly(ethyleneterephthalate), poly(butylene terephthalate), and poly(ethyleneadipate); polyamides such as nylon-6, nylon-6,6, nylon-12, nylon-12,12,nylon-11, and a copolymer of hexamethylene diamine, adipic acid andterephthalic acid; fluorinated polymers such as copolymers of ethyleneand vinylidene fluoride, copolymers of tetrafluoroethylene andhexafluoropropylene, copolymers of tetrafluoroethylene and aperfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), andpoly(vinyl fluoride); other halogenated polymers such a poly(vinylchloride) and poly(vinylidene chloride) and its copolymers; polyolefinssuch as polyethylene, polypropylene and polystyrene, and copolymersthereof; (meth)acrylic polymers such a poly(methyl methacrylate) andcopolymers thereof; copolymers of olefins such as ethylene with various(meth) acrylic monomers such as alkyl acrylates, (meth)acrylic acid andionomers thereof, and glycidyl (meth)acrylate); aromatic polyesters suchas the copolymer of Bisphenol A and terephthalic and/or isophthalicacid; and liquid crystalline polymers such as aromatic polyesters oraromatic poly(ester-amides).

[0753] Suitable thermosets for blending with the polymers describedherein include epoxy resins, phenolformaldehyde resins, melamine resins,and unsaturated polyester resins (sometimes called thermosetpolyesters). Blending with thermoset polymers will often be done beforethe thermoset is crosslinked, using standard techniques.

[0754] The polymers described herein may also be blended withuncrosslinked polymers which are not usually considered thermoplasticsfor various reasons, for instance their viscosity is too high and/ortheir melting point is so high the polymer decomposes below the meltingtemperature. Such polymers include poly(tetrafluoroethylene), aramidssuch as poly(p-phenylene terephthalate) and poly(m-phenyleneisophthalate), liquid crystalline polymer such as poly(benzoxazoles),and non-melt processible polyimides which are often aromatic polyimides.

[0755] All of the polymers disclosed herein may be mixed with variousadditives normally added to elastomers and thermoplastics [see EPSE(below), vol. 14, p. 327-410]. For instance reinforcing, non-reinforcingand conductive fillers, such as carbon black, glass fiber, minerals suchas clay, mica and talc, glass spheres, barium sulfate, zinc oxide,carbon fiber, and aramid fiber or fibrids, may be used. Antioxidants,antiozonants, pigments, dyes, delusterants, compounds to promotecrosslinking may be added. Plasticizers such as various hydrocarbon oilsmay also be used.

[0756] The following listing is of some uses for polyolefins, which aremade from linear olefins and do not include polar monomers such asacrylates, which are disclosed herein. In some cases a reference isgiven which discusses such uses for polymers in general. All of thesereferences are hereby included by reference. For the references, “U”refers to W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of IndustrialChemistry, 5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which thevolume and page number are given, “ECT3” refers to the H. F. Mark, etal., Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., JohnWiley & Sons, New York, “ECT4” refers to the J. I Kroschwitz, et al.,Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., JohnWiley & Sons, New York, for which the volume and page number are given,“EPST” refers to H. F. Mark, et al., Ed., Encyclopedia of PolymerScience and Technology, 1st Ed., John Wiley & Sons, New York, for whichthe volume and page number are given, “EPSE” refers to H. F. Mark, etal., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., JohnWiley & Sons, New York, for which volume and page numbers are given, and“PM” refers to J. A. Brydson, ed., Plastics Materials, 5 Ed.,Butterworth-Heinemann, Oxford, UK, 1989, and the page is given. In theseuses, a polyethylene, polypropylene and a copolymer of ethylene andpropylene are preferred.

[0757] 1. Tackifiers for low strength adhesives (U, vol. Al, p. 235-236)are a use for these polymers. Elastomeric and/or relatively lowmolecular weight polymers are preferred.

[0758] 2. An oil additive for smoke suppression in single-strokegasoline engines is another use. Elastomeric polymers are preferred.

[0759] 3. The polymers are.useful as base resins for hot melt adhesives(U, vol. Al, p. 233-234), pressure sensitive adhesives (U, vol. Al, p.235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives. The polymers may also be used in a carpetinstallation adhesive.

[0760] 4. Lubricating oil additives as Viscosity Index Improvers formultigrade engine oil (ECT3, Vol 14, p. 495-496) are another use.Branched polymers are preferred. Ethylene copolymer with acrylates orother polar monomers will also function as Viscosity Index Improvers formultigrade engine oil with the additional advantage of providing somedispersancy 0.5. Polymer for coatings and/or penetrants for theprotection of various porous items such as lumber and masonry,particularly out-of-doors. The polymer may be in a suspension oremulsion, or may be dissolved in a solvent.

[0761] 6. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

[0762] 7. The polymers may be grafted with various compoundsparticularly those that result in functional groups such as epoxy,carboxylic anhydride (for instance as with a free radically polymerizedreaction with maleic anhydride) or carboxylic acid (EPSE, vol. 12, p.445). Such functionalized polymers are particularly useful as toughenersfor various thermoplastics and thermosets when blended. When thepolymers are elastomers, the functional groups which are grafted ontothem may be used as curesites to crosslink the polymers. Maleicanhydride-grafted randomly-branched polyolefins are useful as toughenersfor a wide range of materials (nylon, PPO, PPO/styrene alloys, PET, PBT,POM, etc.); as tie layers in multilayer constructs such as packagingbarrier films; as hot melt, moisture-curable, and coextrudableadhesives; or as polymeric plasticizers. The maleic and hydride-graftedmaterials may be post reacted with, for example; amines, to form otherfunctional materials. Reaction with aminopropyl trimethoxysilane wouldallow for moisture-curable materials. Reactions with di- and tri-amineswould allow for viscosity modifications.

[0763] 8. The polymers, particularly elastomers, may be used formodifying asphalt, to improve the physical properties of the asphaltand/or extend the life of asphalt paving.

[0764] 9. The polymers may be used as base resins for chlorination orchlorosulfonation for making the corresponding chlorinated orchlorosulfonated elastomers. The unchlorinated polymers need not beelastomers themselves.

[0765] 10. Wire insulation and jacketing may be made from any of thepolyolefins (see EPSE, vol. 17, p. 828-842). In the case of elastomersit may be preferable to crosslink the polymer after the insulation orjacketing is formed, for example by free radicals.

[0766] 11. The polymers, particularly the elastomers, may be used astougheners for other polyolefins such as polypropylene and polyethylene.

[0767] 12. The base for synthetic lubricants (motor oils) may be thehighly branched polyolefins described herein (ECT3, vol. 14, p.496-501).

[0768] 13. The branched polyolefins herein can be used as dripsuppressants when added to other polymers.

[0769] 14. The branched polyolefins herein are especially useful inblown film applications because of their particular rheologicalproperties (EPSE, vol. 7, p. 88-106). It is preferred that thesepolymers have some crystallinity.

[0770] 15. The polymer described herein can be used to blend with waxfor candles, where they would provide smoke suppression and/or dripcontrol.

[0771] 16. The polymers, especially the branched polymers, are useful asbase resins for carpet backing, especially for automobile carpeting.

[0772] 17. The polymers, especially those which are relatively flexible,are useful as capliner resins for carbonated and noncarbonatedbeverages.

[0773] 18. The polymers, especially those having a relatively lowmelting point, are useful as thermal transfer imaging resins (forinstance for imaging teeshirts or signs)

[0774] 19. The polymers may be used for extrusion or coextrusioncoatings onto plastics, metals, textiles or paper webs.

[0775] 20. The polymers may be used as a laminating adhesive for glass.

[0776] 21. The polymers are useful as for blown or cast films or assheet (see EPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252and p. 432ff). The films may be single layer or multilayer, themultilayer films may include other polymers, adhesives, etc. Forpackaging the films may be stretch-wrap, shrink-wrap or cling wrap. Thefilms are useful form many applications such as packaging foods,geomembranes and pond liners. It is preferred that these polymers havesome crystallinity.

[0777] 22. The polymers may be used to form flexible or rigid foamedobjects, such as cores for various sports items such as surf boards andliners for protective headgear. Structural foams may also be made. It ispreferred that the polymers have some crystallinity. The polymer of thefoams may be crosslinked.

[0778] 23. In powdered form the polymers may be used to coat objects byusing plasma, flame spray or fluidized bed techniques.

[0779] 24. Extruded films may be formed from these polymers, and thesefilms may be treated, for example drawn. Such extruded films are usefulfor packaging of various sorts.

[0780] 25. The polymers, especially those that are elastomeric, may beused in various types of hoses, such as automotive heater hose.

[0781] 26. The polymers, especially those that are branched, are usefulas pour point depressants for fuels and oils.

[0782] 27. These polymers may be flash spun to nonwoven fabrics,particularly if they are crystalline (see EPSE vol. 10, p. 202-253) Theymay also be used to form spunbonded polyolefins (EPSE, vol. 6, p.756-760). These fabrics are suitable as house wrap and geotextiles.

[0783] 28. The highly branched, low viscosity polyolefins would be goodas base resins for master-batching of pigments, fillers,flame-retardants, and related additives for polyolefins. 29. Thepolymers may be grafted with a compound containing ethylenicunsaturation and a functional group such as a carboxyl group or aderivative of a carboxyl group, such as ester, carboxylic anhydride ofcarboxylate salt. A minimum grafting level of about 0.01 weight percentof grafting agent based on the weight of the grafted polymer ispreferred. The grafted polymers are useful as compatibilizers and/ortougheners. Suitable grafting agents include maleic, acrylic,methacrylic, itaconic, crotonic, alpha-methyl crotonic and cinnamicacids, anhydrides, esters and their metal salts and fumaric acid andtheir esters, anhydrides (when appropriate) and metal salts.

[0784] Copolymers of linear olefins with 4-vinylcyclohexene and otherdienes may generally be used for all of the applications for which thelinear olefins polymers(listed above) may be used. In addition they maybe sulfur cured, so they generally can be used for any use for whichEPDM polymers are used, assuming the olefin/4-vinylcyclohexene polymeris elastomeric.

[0785] Also described herein are novel copolymers of linear olefins withvarious polar monomers such as acrylic acid and acrylic esters. Uses forthese polymers are given below. Abbreviations for references describingthese uses in general with polymers are the same as listed above forpolymers made from linear olefins.

[0786] 1. Tackifiers for low strength adhesives (U, vol. Al, p. 235-236)are a use for these polymers. Elastomeric and/or relatively lowmolecular weight polymers are preferred.

[0787] 2. The polymers are useful as base resins for hot melt adhesives(U, vol. Al, p. 233-234), pressure sensitive adhesives (U, vol. Al, p.235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives. The polymers may also be used in a carpetinstallation adhesive.

[0788] 3. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

[0789] 4. The polymers, particularly elastomers, may be used formodifying asphalt, to improve the physical properties of the asphaltand/or extend the life of asphalt paving, see U.S. Pat. No. 3,980,598.

[0790] 5. Wire insulation and jacketing may be made from any of thepolymers (see EPSE, Vol. 17, p. 828-842). In the case of elastomers itmay be preferable to crosslink the polymer after the insulation orjacketing is formed, for example by free radicals.

[0791] 6. The polymers, especially the branched polymers, are useful asbase resins for carpet backing, especially for automobile carpeting.

[0792] 7. The polymers may be used for extrusion or coextrusion coatingsonto plastics, metals, textiles or paper webs.

[0793] 8. The polymers may be used as a laminating adhesive for glass.

[0794] 9. The polymers are useful as for blown or cast films or as sheet(see EPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 andp. 432ff). The films may be single layer or multilayer, the multilayerfilms may include other polymers, adhesives, etc. For packaging thefilms may be stretch-wrap, shrink-wrap or cling wrap. The films areuseful form many applications such as packaging foods, geomembranes andpond liners. It is preferred that these polymers have somecrystallinity.

[0795] 10. The polymers may be used to form flexible or rigid foamedobjects, such as cores for various sports items such as surf boards andliners for protective headgear. Structural foams may also be made. It ispreferred that the polymers have some crystallinity. The polymer of thefoams may be crosslinked.

[0796] 11. In powdered form the polymers may be used to coat objects byusing plasma, flame spray or fluidized bed techniques.

[0797] 12. Extruded films may be formed from these polymers, and thesefilms may be treated, for example drawn. Such extruded films are usefulfor packaging of various sorts.

[0798] 13. The polymers, especially those that are elastomeric, may beused in various types of hoses, such as automotive heater hose.

[0799] 14. The polymers may be used as reactive diluents in automotivefinishes, and for this purpose it is preferred that they have arelatively low molecular weight and/or have some crystallinity.

[0800] 15. The polymers can be converted to ionomers, which when thepossess crystallinity can be used as molding resins. Exemplary uses forthese ionomeric molding resins are golf ball covers, perfume caps,sporting goods, film packaging applications, as tougheners in otherpolymers, and usually extruded) detonator cords.

[0801] 16. The functional groups on the polymers can be used to initiatethe polymerization of other types of monomers or to copolymerize withother types of monomers. If the polymers are elastomeric, they can actas toughening agents.

[0802] 17. The polymers can act as compatibilizing agents betweenvarious other polymers.

[0803] 18. The polymers can act as tougheners for various otherpolymers, such as thermoplastics and thermosets, particularly if theolefin/polar monomer polymers are elastomeric.

[0804] 19. The polymers may act as internal plasticizers for otherpolymers in blends. A polymer which may be plasticized is poly(vinylchloride).

[0805] 20. The polymers can serve as adhesives between other polymers.

[0806] 21. With the appropriate functional groups, the polymers mayserve as curing agents for other polymers with complimentary functionalgroups (i.e., the functional groups of the two polymers react with eachother).

[0807] 22. The polymers, especially those that are branched, are usefulas pour point depressants for fuels and oils.

[0808] 23. Lubricating oil additives as Viscosity Index Improvers formultigrade engine oil (ECT3, Vol 14, p. 495-496) are another use.Branched polymers are preferred. Ethylene copolymer with acrylates orother polar monomers will also function as Viscosity Index Improvers formultigrade engine oil with the additional advantage of providing somedispersancy.

[0809] 24. The polymers may be used for roofing membranes.

[0810] 25. The polymers may be used as additives to various moldingresins such as the so-called thermoplastic olefins to improve paintadhesion, as in automotive uses.

[0811] Polymers with or without polar monomers present are useful in thefollowing uses. Preferred polymers with or without polar monomers arethose listed above in the uses for each “type”.

[0812] 1. A flexible pouch made from a single layer or multilayer film(as described above) which may be used for packaging various liquidproducts such as milk, or powder such as hot chocolate mix. The pouchmay be heat sealed. It may also have a barrier layer, such as a metalfoil layer.

[0813] 2. A wrap packaging film having differential cling is provided bya film laminate, comprising at least two layers; an outer reverse whichis a polymer (or a blend thereof) described herein, which contains atackifier in sufficent amount to impart cling properties; and an outerobverse which has a density of at least about 0.916 g/mL which haslittle or no cling, provided that a density of the outer reverse layeris at least 0.008 g/mL less than that of the density of the outerobverse layer. It is preferred that the outer obverse layer is linearlow density polyethylene, and the polymer of the outer obverse layerhave a density of less than 0.90 g/mL. All densities are measured at 25°C.

[0814] 3. Fine denier fibers and/or multifilaments. These may be meltspun. They may be in the form of a filament bundle, a non-woven web, awoven fabric, a knitted fabric or staple fiber.

[0815] 4. A composition comprising a mixture of the polymers herein andan antifogging agent. This composition is especially useful in film orsheet form because of its antifogging properties.

[0816] 5. Elastic, randomly-branched olefin polymers are disclosed whichhave very good processability, including processing indices (PI's) lessthan or equal to 70 percent of those of a comparative linear olefinpolymer and a critical shear rate at onset of surface melt fracture ofat least 50 percent greater than the critical shear rate at the onset ofsurface melt fracture of a traditional linear olefin polymer at aboutthe same I2 and Mw/Mn. The novel polymers may have higher low/zero shearviscosity and lower high shear viscosity than comparative linear olefinpolymers made by other means. These polymers may be characterized ashaving: a) a melt flow ratio, I10/I2, ≧5.63, b) a molecular weightdistribution, Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)−4.63, andc) a critical shear rate at onset of surface melt fracture of at least50 percent greater than the critical shear rate at the onset of surfacemelt fracture of a linear olefin polymer having about the same I2 andMw/Mn. Some blends of these polymer are characterized as having: a) amelt flow ratio, I10/I2, ≧5.63, b) a molecular weight distribution,Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)−4.63, and c) a criticalshear rate at onset of surface melt fracture of at least 50 percentgreater than the critical shear rate at the onset of surface meltfracture of a linear olefin polymer having about the same I2 and Mw/Mnand (b) at least one other natural or synthetic polymer chosen from thepolymer of claims 1, 3, 4, 6, 332, or 343, a conventional high densitypolyethylene, low density polyethylene or linear low densitypolyethylene polymer. The polymers may be further characterized ashaving a melt flow ratio, I10/I2, ≧5.63, a molecular weightdistribution, Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)−4.63, and acritical shear stress at onset of gross melt fracture of greater thanabout 400 kPa (4×10⁶ dyne/cm²) and their method of manufacture aredisclosed. The randomly-branched olefin polymers preferably have amolecular weight distribution from about 1.5 to about 2.5. The polymersdescribed herein often have improved processability over conventionalolefin polymers and are useful in producing fabricated articles such asfibers, films, and molded parts. For this paragraph, the value I2 ismeasured in accordance with ASTM D-1238-190/2.16 and I10 is measured inaccordance with ASTM D-1238-190/10; critical shear rate at onset ofsurface melt fracture and processing index (PI) are defined in U.S. Pat.No. 5,278,272, which is hereby included by reference.

[0817] In another process described herein, the product of the processdescribed herein is an α-olefin. It is preferred that in the process alinear α-olefin is produced. It is also preferred that the α-olefincontain 4 to 32, preferably 8 to 20, carbon atoms.

[0818] When (XXXI) is used as a catalyst, a neutral Lewis acid or acationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion is also present as part of the catalyst system(sometimes called a “first compound” in the claims). By a “neutral Lewisacid” is meant a compound which is a Lewis acid capable for abstractingX⁻ from (I) to form a weakly coordinating anion. The neutral Lewis acidis originally uncharged (i.e., not ionic). Suitable neutral Lewis acidsinclude SbF₅, Ar₃B (wherein Ar is aryl), and BF₃. By a cationic Lewisacid is meant a cation with a positive charge such as Ag⁺, H⁺, and Na⁺.

[0819] A preferred neutral Lewis acid is an alkyl aluminum compound,such as R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlC₂, and “R⁹AlO” (alkylaluminoxane),wherein R⁹ is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4carbon atoms. Suitable alkyl aluminum compounds includemethylaluminoxane, (C₂H₅)₂AlCl, C₂H₅AlCl₂, and [(CH₃)₂CHCH₂]₃Al.

[0820] Relatively noncoordinating anions are known in the art, and thecoordinating ability of such anions is known and has been discussed inthe literature, see for instance W. Beck., et al., Chem. Rev., vol. 88p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942(1993), both of which are hereby included by reference. Among suchanions are those formed from the aluminum compounds in the immediatelypreceding paragraph and X⁻, including R⁹ ₃AlX⁻, R⁹ ₂AlClX⁻, R⁹AlCl₂X⁻,and “R⁹AlOX⁻”. Other useful noncoordinating anions include BAF⁻{BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF₆ ⁻, PF₆ ⁻, andBF₄ ⁻, trifluoromethanesulfonate, p-toluenesulfonate, (R_(f)SO₂)₂N⁻, and(C₆F₅)₄B⁻.

[0821] The temperature at which the process is carried out is about−100° C. to about +200° C., preferably about 0° C. to about 150° C.,more preferably about 25° C. to about 100° C. It is believed that athigher temperatures, lower molecular weight α-olefins are produced, allother factors being equal. The pressure at which the polymerization iscarried out is not critical, atmospheric pressure to about 275 MPa beinga suitable range. It is also believed that increasing the pressureincreases the relative amount of α-olefin (as opposed to internalolefin) produced.

[0822] The process to make α-olefins may be run in a solvent (liquid),and that is preferred. The solvent may in fact be the α-olefin produced.Such a process may be started by using a deliberately added solventwhich is gradually displaced as the reaction proceeds. By solvent it isnot necessarily meant that any or all of the starting materials and/orproducts are soluble in the (liquid) solvent.

[0823] In (I) it is preferred that R³ and R⁴ are both hydrogen or methylor R³ and R⁴ taken together are

[0824] It is also preferred that each of Q and S is independentlychlorine or bromine, and it is more preferred that both of Q and S in(XXXI) are chlorine or bromine.

[0825] In (XXXI) R² and R⁵ are hydrocarbyl or substituted hydrocarbyl.What these groups are greatly determines whether the α-olefins of thisprocess are made, or whether higher polymeric materials, i.e., materialscontaining over 25 ethylene units, are coproduced or produced almostexclusively. If R² and R⁵ are highly sterically hindered about thenickel atom, the tendency is to produce higher polymeric material. Forinstance, when R² and R⁵ are both 2,6-diisopropylphenyl mostly higherpolymeric material is produced. However, when R² and R⁵ are both phenyl,mostly the α-olefins of this process are produced. Of course this willalso be influenced by other reaction conditions such as temperature andpressure, as noted above. Useful groups for R² and R⁵ are phenyl, andp-methylphenyl.

[0826] As is understood by the artisan, in oligomerization reactions ofethylene to produce aolefins, usually a mixture of such α-olefins isobtained containing a series of such α-olefins differing from oneanother by two carbon atoms (an ethylene unit). The process forpreparing α-olefins described herein produces products with a highpercentage of terminal olefinic groups (as opposed to internal olefinicgroups). The product mixture also contains a relatively high percentageof molecules which are linear. Finally relatively high catalystefficiencies can be obtained.

[0827] The α-olefins described as being made herein may also be made bycontacting ethylene with one of the compounds

[0828] wherein R², R³, R⁴, and R⁵ are as defined (and preferred) asdescribed above (for the preparation of α-olefins), and T¹ is hydrogenor n-alkyl containing up to 38 carbon atoms, Z is a neutral Lewis basewherein the donating atom is nitrogen, sulfur, or oxygen, provided thatif the donating atom is nitrogen then the pKa of the conjugate acid ofthat compound (measured in water) is less than about 6, U is n-alkylcontaining up to 38 carbon atoms, and X is a noncoordinating anion (seeabove). The process conditions for making α-olefins using (III) or(XXXIV) are the same as for using (XXXI) to make these compounds excepta Lewis or Bronsted acid need not be present. Note that the double linein (XXXIV) represents a coordinated ethylene molecule. (XXXIV) may bemade from (II) by reaction of (III) with ethylene. In other words,(XXXIV) may be considered an active intermediate in the formation ofα-olefin from (III). Suitable groups for Z include dialkyl ethers suchas diethyl ether, and alkyl nitriles such as acetonitrile.

[0829] In general, α-olefins can be made by this process using as acatalyst a Ni[II] complex of an α-diimine of formula (VIII), wherein theNi[II] complex is made by any of the methods which are described above,using Ni[0], Ni[I] or Ni[II] precursors. All of the process conditions,and preferred groups on (VIII), are the same as described above in theprocess for making α-olefins.

EXAMPLES

[0830] In the Examples, the following convention is used for namingα-diimine complexes of metals, and the α-diimine itself. The α-diimineis indicated by the letters “DAB”. To the left of the “DAB” are the twogroups attached to the nitrogen atoms, herein usually called R² and R⁵.To the right of the “DAB” are the groups on the two carbon atoms of theα-diimine group, herein usually termed R³ and R⁴. To the right of allthis appears the metal, ligands attached to the metal (such as Q, S andT), and finally any anions (X), which when “free” anions are designatedby a superscript minus sign (i.e., X⁻). of course if there is a “free”anion present, the metal containing moiety is cationic. Abbreviationsfor these groups are as described in the Specification in the Note afterTable 1. Analogous abbreviations are used for α-diimines, etc.

[0831] In the Examples, the following abbreviations are used:

[0832] ΔH_(f)-heat of fusion

[0833] acac-acetylacetonate

[0834] Bu-butyl

[0835] t-BuA-t-butyl acrylate

[0836] DMA-Dynamic Mechanical Analysis

[0837] DME-1,2-dimethoxyethane

[0838] DSC-Differential Scanning Calorimetry

[0839] E-ethylene

[0840] EOC-end of chain

[0841] Et-ethyl

[0842] FC-75-perfluoro(n-butyltetrahydrofuran)

[0843] FOA-fluorinated octyl acrylate

[0844] GPC-gel permeation chromatography

[0845] MA-methyl acrylate

[0846] MAO-methylaluminoxane

[0847] Me-methyl

[0848] MeOH-methanol

[0849] MMAO-a modified methylaluminoxane in which about 25 mole percentof the methyl groups have been replaced by isobutyl groups

[0850] M-MAO-see MMAO

[0851] MMAO-3A-see MMAO

[0852] Mn-number average molecular weight

[0853] MVK-methyl vinyl ketone

[0854] Mw-weight average molecular weight

[0855] Mz-viscosity average molecular weight

[0856] PD or P/D-polydispersity, Mw/Mn

[0857] Ph-phenyl

[0858] PMAO-see MAO

[0859] PMMA-poly(methyl methacrylate)

[0860] Pr-propyl

[0861] PTFE-polytetrafluoroethylene

[0862] RI-refractive index

[0863] RT (or rt)-room temperature

[0864] TCE-1,1,2,2-tetrachloroethane

[0865] Tc-temperature of crystallization

[0866] Td-temperature of decomposition

[0867] Tg-glass transition temperature

[0868] TGA-Thermogravimetric Analysis

[0869] THF-tetrahydrofuran

[0870] Tm-melting temperature

[0871] TO-turnovers, the number of moles of monomer polymerized perg-atom of metal in the catalyst used

[0872] UV-ultraviolet

[0873] Unless otherwise noted, all pressures are gauge pressures.

[0874] In the Examples, the following procedure was used toquantitatively determine branching, and the distribution of branch sizesin the polymers (but not necessarily the simple number of branches asmeasured by total number of methyl groups per 1000 methylene groups).100 MHz ¹³C NMR spectra were obtained on a Varian Unity 400 MHzspectrometer using a 10 mm probe on typically 15-20 wt % solutions ofthe polymers and 0.05 M Cr(acetylacetonate)₃ in 1,2,4-trichlorobenzene(TCB) unlocked at 120-140° C. using a 90 degree pulse of 12.5 to 18.5μsec, a spectral width of 26 to 35 kHz, a relaxation delay of 5-9 s, anacquisition time of 0.64 sec and gated decoupling. Samples werepreheated for at least 15 min before acquiring data. Data acquisitiontime was typically 12 hr. per sample. The T¹ values of the carbons weremeasured under these conditions to be all less than 0.9 s. The longestT¹ measured was for the Bu⁺, end of chain resonance at 14 ppm, which was0.84 s. Occasionally about 16 vol. % benzene-d₆ was added to the TCB andthe sample was run locked. Some samples were run in chloroform-d1,CDCl₃-d1, (locked) at 30° C. under similar acquisition parameters. T¹′swere also measured in CDCl₃ at ambient temperature on a typical samplewith 0.05 M Cr(acetylacetonate)₃ to be all less than 0.68 s. In rarecases when Cr(acetylacetonate)₃ was not used, a 30-40 s recycle delaywas used to insure quantitation. The glycidyl acrylate copolymer was runat 100° C. with Cr(acetylacetonate)₃. Spectra are referenced to thesolvent—either the TCB highfield resonance at 127.8 ppm or thechloroform-d1 triplet at 77 ppm. A DEPT 135 spectrum was done on mostsamples to distinguish methyls and methines from methylenes. Methylswere distinguished from methines by chemical shift. EOC is end-of-chain.Assignments reference to following naming scheme:

[0875] 1. xBy: By is a branch of length y carbons; x is the carbon beingdiscussed, the methyl at the end of the branch is numbered 1. Thus thesecond carbon from the end of a butyl branch is 2B4. Branches of lengthy or greater are designated as y⁺.

[0876] 2. xEBy: EB is an ester ended branch containing y methylenes. xis the carbon being discussed, the first methylene adjacent to the estercarbonyl is labeled 1. Thus the second methylene from the end of a 5methylene ester terminated branch would be 2EB5. ¹³C NMR of modelcompounds for EBy type branches for y=0 and y=5⁺ confirm the peakpositions and assignments of these branches. In addition, a modelcompound for an EB1 branch is consistent with 2 dimensional NMR datausing the well know 2D NMR techniques of hsqc, hmbc, and hsqc-tocsy; the2D data confirms the presence of the EB5⁺, EB0, EB1 and otherintermediate length EB branches

[0877] 3. The methylenes in the backbone are denoted with Greek letterswhich determine how far from a branch point methine each methylene is.Thus ββ (beta beta) B denotes the central methylene in the followingPCHRCH₂CH₂CH₂CHRP. Methylenes that are three or more carbons from abranch point are designated as δ⁺ (gamma⁺).

[0878] 4. When x in xBy or xEBy is replaced by a M, the methine carbonof that branch is denoted.

[0879] Integrals of unique carbons in each branch were measured and werereported as number of branches per 1000 methylenes (including methylenesin the backbone and branches). These integrals are accurate to +/− 5%relative for abundant branches and +/− 10 or 20% relative for branchespresent at less than 10 per 1000 methylenes.

[0880] Such types of analyses are generally known, see for instance “AQuantitative Analysis of Low Density (Branched) Polyethylenes byCarbon-13 Fourier Transform Nuclear Magnetic Resonance at 67.9 MHz”, D.E. Axelson, et al., Macromolecules 12 (1979) pp. 41-52; “Fine BranchingStructure in High-Pressure, Low Density Polyethylenes by 50.10-MHz ¹³CNMR Analysis”, T. Usami et al., Macromolecules 17 (1984) pp. 1757-1761;and “Quantification of Branching in Polyethylene by ¹³C NMR UsingParamagnetic Relaxation Agents”, J. V. Prasad, et al., Eur. Polym. J. 27(1991) pp. 251-254 (Note that this latter paper is believed to have somesignificant typographical errors in it).

[0881] It is believed that in many of the polymers described hereinwhich have unusual branching, i.e., they have more or fewer branchesthan would be expected for “normal” coordination polymerizations, or thedistribution of sizes of the branches is different from that expected,that “branches on branches” are also present. By this is meant that abranch from the main chain on the polymer may itself contain one or morebranches. It is also noted that the concept of a “main chain” may be asomewhat semantic argument if there are sufficient branches on branchesin any particular polymer.

[0882] By a polymer hydrocarbyl branch is meant a methyl group to amethine or quaternary carbon atom or a group of consecutive methylenesterminated at one end by a methyl group and connected at the other endto a methine or quaternary carbon atom. The length of the branch isdefined as the number of carbons from and including the methyl group tothe nearest methine or quaternary carbon atom, but not including themethine or quaternary carbon atom. If the number of consecutivemethylene groups is “n” then the branch contains (or the branch lengthis) n+1. Thus the structure (which represents part of a polymer)—CH₂CH₂CH[CH₂CH₂CH₂CH₂CH(CH₃)CH₂CH₃]CH₂CH₂CH₂CH₂— contains 2 branches, amethyl and an ethyl branch.

[0883] For ester ended branches a similar definition is used. An esterbranch refers to a group of consecutive methylene groups terminated atone end by an ester —COOR group, and connected at the other end to amethine or quaternary carbon atom. The length of the branch is definedas the number of consecutive methylene groups from the ester group tothe nearest methine or quaternary carbon atom, but not including themethine or quaternary carbon atom. If the number of methylene groups is“n”, then the length of the branch is n. Thus—CH₂CH₂CH[CH₂CH₂CH₂CH₂CH(CH₃)CH₂COOR]CH₂CH₂CH₂CH₂— contains 2 branches,a methyl and an n=1 ester branch.

[0884] The ¹³C NMR peaks for copolymers of cyclopentene and ethylene aredescribed based on the labeling scheme and assignments of A. Jerschow etal, Macromolecules 1995, 28, 7095-7099. The triads and pentads aredescribed as 1-cme, 1,3-ccmcc, 1,3-cmc, 2-cme, 2-cmc, 1,3-eme,3-cme, and4,5-cmc, where e=ethylene, c=cyclopentene, and m=meta cyclopentene (i.e.1,3 enchainment). The same labeling is used for cyclopentene/1-pentenecopolymer substituting p=pentene for e. The synthesis of diimines isreported in the literature (Tom Dieck, H.; Svoboda, M.; Grieser, T. Z.Naturforsch 1981, 36b, 823-832. Kliegman, J. M.; Barnes, R. K. J. Org.Chem. 1970, 35, 3140-3143.)

Example 1 [(2,6-i-PrPh)₂DABMe₂]PdMeCl

[0885] Et₂O (75 mL) was added to a Schlenk flask containing CODPdMeCl(COD=1,5-cyclooctadiene) (3.53 g, 13.3 mmol) and a slight excess of(2,6-i-PrPh)₂DABMe₂ (5.43 g, 13.4 mmol, 1.01 equiv). An orangeprecipitate began to form immediately upon mixing. The reaction mixturewas stirred overnight and the Et₂O and free COD were then removed viafiltration. The product was washed with an additional 25 mL of Et₂O andthen dried overnight in vacuo. A pale orange powder (7.18 g, 95.8%) wasisolated: ¹H NMR (CD₂Cl₂, 400 MHz) δ7.4-7.2 (m, 6, H_(aryl)), 3.06(septet, 2, J=6.81, CHMe₂), 3.01 (septet, 2, J=6.89, C′HMe₂), 2.04 and2.03 (N═C(Me)—C′ (Me)═N), 1.40 (d, 6, J=6.79, C′HMeMe′), 1.36 (d, 6,J=6.76, CHMeMe′), 1.19 (d, 6, J=6.83, CHMeMe′), 1.18 (d, 6, J=6.87,C′HMeMe′), 0.36 (s, 3, PdMe); ¹³C NMR (CD₂Cl₂, 400 MHz) δ175.0 and 170.3(N═C—C′═N), 142.3 and 142.1 (Ar, Ar′: C_(ipso)), 138.9 and 138.4 (Ar,Ar′: C_(o)), 128.0 and 127.1 (Ar, Ar′: C_(p)), 124.3 and 123.5 (Ar, Ar′:C_(m)), 29.3 (CHMe₂), 28.8 (C′HMe₂), 23.9, 23.8, 23.5 and 23.3 (CHMeMe′,C′HMeMe′), 21.5 and 20.1 (N═C(Me)—C′ (Me)═N), 5.0 (J_(CH)=135.0, PdMe).

Example 2 [(2,6-i-PrPh)₂DABH₂]PdMeCl

[0886] Following the procedure of Example 1, an orange powder wasisolated in 97.1% yield: ¹H NMR (CD₂Cl₂, 400 MHz) δ8.31 and 8.15 (s, 1each, N═C(H)—C′(H)═N), 7.3-7.1 (m, 6, H_(aryl)), 3.22 (septet, 2,J=6.80, CHMe₂), 3.21 (septet, 2, J=6.86, C′HMe₂), 1.362, 1.356, 1.183and 1.178 (d, 6 each, J=7.75-6.90; CHMeMe′, C′HMeMe′), 0.67 (s, 3,PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz) δ164.5 (J_(CH)=179.0, N═C(H)), 160.6(J_(CH)=178.0, N═C′(H)), 144.8 and 143.8 (Ar, Ar′: C_(ipso)), 140.0 and139.2 (Ar, Ar′: C_(o)), 128.6 and 127.7 (Ar, Ar′: C_(p)), 124.0 and123.4 (Ar, Ar′: C_(m)), 29.1 (CHMe₂), 28.6 (C′HMe₂), 24.7, 24.1, 23.1and 22.7 (CHMeMe′, C′HMeMe′), 3.0 (J_(CH)=134.0, PdMe). Anal. Calcd for(C₂₇H₃₉ClN₂Pd): C, 60.79; H, 7.37; N, 5.25. Found: C, 60.63; H, 7.24; N,5.25.

Example 3 [(2,6-MePh)₂DABMe₂]PdMeCl

[0887] Following the procedure of Example 1, a yellow powder wasisolated in 90.6% yield: ¹H NMR (CD₂Cl₂, 400 MHz) δ7.3-6.9 (m, 6,H_(aryl)), 2.22 (s, 6, Ar, Ar′: Me), 2.00 and 1.97 (N═C(Me)—C′(Me)═N),0.25 (s, 3, PdMe).

Example 4 [(2,6-MePh)₂DABMe₂]PdMeCl

[0888] Following the procedure of Example 1, an orange powder wasisolated in 99.0% yield: ¹H NMR (CD₂Cl₂, 400 MHz, 41° C.) δ8.29 and 8.14(N═C(H)—C′(H)═N), 7.2-7.1 (m, 6, H_(aryl)), 2.33 and 2.30 (s, 6 each,Ar, Ar′: Me), 0.61 (s, 3, PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz, 41° C.)δ165.1 (J_(CH)=179.2, N═C(H)), 161.0 (J_(CH)=177.8 (N═C′(H)), 147.3 and146.6 (Ar, Ar′: C_(ipso)), 129.5 and 128.8 (Ar, Ar′: C_(o)), 128.8 and128.5 (Ar, Ar′: C_(m)), 127.9 and 127.3 (Ar, Ar′: C_(p)), 18.7 and 18.2(Ar, Ar′: Me), 2.07 (J_(CH)=136.4, PdMe).

Example 5 [4-MePh)₂DABMe₂]PdMeCl

[0889] Following the procedure of Example 1, a yellow powder wasisolated in 92.1% yield: ¹H NMR (CD₂Cl₂, 400 MHz) δ7.29 (d, 2, J=8.55,Ar: H_(m)), 7.26 (d, 2, J=7.83, Ar′: H_(m)), 6.90 (d, 2, J=8.24, Ar′:H_(o)), 6.83 (d, 2, J=8.34, Ar: H_(o)), 2.39 (s, 6, Ar, Ar′: Me), 2.15and 2.05 (s, 3 each, N═C(Me)—C′(Me)═N), 0.44 (s, 3, PdMe); ¹³C NMR(CD₂Cl₂, 100 MHz) δ176.0 and 169.9 (N═C—C′═N), 144.9 and 143.7 (Ar, Ar′:C_(ipso)), 137.0 and 136.9 (Ar, Ar′: C_(p)), 130.0 and 129.3 (Ar, Ar′:C_(m)), 122.0 and 121.5 (Ar, Ar′: C_(o)), 21.2 (N═C(Me)), 20.1 (Ar, Ar′:Me), 19.8 (N═C′(Me)), 2.21 (J_(CH)=135.3, PdMe). Anal. Calcd for(C₁₉H₂₃ClN₂Pd): C, 54.17; H, 5.50; N, 6.65. Found: C, 54.41; H, 5.37; N,6.69.

Example 6 [(4-MePh)₂DABH₂]PdMeCl

[0890] Following the procedure of Example 1, a burnt orange powder wasisolated in 90.5% yield: Anal. Calcd for (C₁₇H₁₉ClN₂Pd): C, 51.93; H,4.87; N, 7.12. Found: C, 51.36; H, 4.80; N, 6.82.

Example 7 <{[(2,6-i-PrPh)₂DABMe₂PdMe}₂(μ-Cl)>BAF⁻

[0891] Et₂O (25 mL) was added to a mixture of[(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.81 g, 1.45 mmol) and 0.5 equiv of NaBAF(0.64 g, 0.73 mmol) at room temperature. A golden yellow solution andNaCl precipitate formed immediately upon mixing. The reaction mixturewas stirred overnight and then filtered. After the Et₂O was removed invacuo, the product was washed with 25 mL of hexane. The yellow powderwas then dissolved in 25 mL of CH₂Cl₂ and the resulting solution wasfiltered in order to removed traces of unreacted NaBAF. Removal ofCH₂Cl₂ in vacuo yielded a golden yellow powder (1.25 g, 88.2%): ¹H NMR(CD₂Cl₂, 400 MHz) δ7.73 (s, 8, BAF: H_(o)), 7.57 (s, 4, BAF: H_(p)),7.33 (t, 2, J=7.57, Ar: H_(p)), 7.27 (d, 4, J=7.69, Ar: H_(o)), 7.18 (t,2, J=7.64, Ar: H_(p)), 7.10 (d, 4, J=7.44, Ar′: H_(o)), 2.88 (septet, 4,J=6.80, CHMe₂), 2.75 (septet, 4, J=6.82, C′HMe₂), 2.05 and 2.00 (s, 6each, N═C(Me)—C′(Me)═N), 1.22, 1.13, 1.08 and 1.01 (d, 12 each,J=6.61-6.99, CHMeMe′, C′HMeMe′), 0.41 (s, 6, PdMe); ¹³C NMR (CD₂Cl₂, 100MHz) δ177.1 and 171.2 (N═C—C′═N), 162.2 (q, J_(BC)=49.8, BAF: C_(ipso)),141.4 and 141.0 (Ar, Ar′: C_(ipso)), 138.8 and 138.1 (Ar, Ar′: C_(o)),135.2 (BAF: C_(p)), 129.3 (q, J_(CF)=31.6, BAF: C_(m)), 128.6 and 127.8(Ar, Ar′: C_(p)), 125.0 (q, J_(CF)=272.5, BAF: CF₃), 124.5 and 123.8(Ar, Ar′: C_(m)), 117.9 (BAF: C_(p)), 29.3 (CHMe₂), 29.0 (C′HMe₂), 23.8,23.7, 23.6 and 23.0 (CHMeMe′, C′HMeMe′), 21.5 and 20.0(N═C(Me)—C′(Me)═N), 9.8 (J_(CH)=136.0, PdMe). Anal. Calcd for(C₉₀OH₉₈BClF₂₄N₄Pd₂): C, 55.41; H, 5.06; N, 2.87. Found: C, 55.83; H,5.09; N, 2.63.

Example 8 <{[(2,6-i-PrPh)₂DABH₂]PdMe}₂(μ-Cl)>BAF⁻

[0892] The procedure of Example 7 was followed with one exception, theremoval of CH₂Cl₂ in vacuo yielded a product that was partially an oil.Dissolving the compound in Et₂O and then removing the Et₂O in vacuoyielded a microcrystalline red solid (85.5%): ¹H NMR (CD₂Cl₂, 400 MHz)δ8.20 and 8.09 (s, 2 each, N═C(H)—C′(H)═N), 7.73 (s, 8, BAF: H_(o)),7.57 (s, 4, BAF: H_(p)), 7.37 (t, 2, J=7.73, Ar: H_(p)), 7.28 (d, 4,J=7.44, Ar: H_(m)), 7.24 (t, 2, Ar′: H_(p)), 7.16 (d, 4, J=7.19, Ar′:H_(m)), 3.04 (septet, 4, J=6.80, CHMe₂), 2.93 (septet, 4, J=6.80,C′HMe₂), 1.26 (d, 12, J=6.79, CHMeMe′), 1.14 (d, 12, J=6.83, CHMeMe′),1.11 (d, 12, J=6.80, C′HMeMe′), 1.06 (d, 12, J=6.79, C′HMeMe′), 0.74 (s,6, PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz) δ166.0 (J_(CH)=180.4, N═C(H)), 161.9(q, J_(BC)=49.6, BAF: C_(ipso)), 160.8 (J_(CH)=179.9, N═C′(H)), 143.5and 143.0 (Ar, Ar′: C_(ipso)), 139.8 and 138.9 (Ar, Ar′: C_(o)), 135.2(BAF: C_(o)), 129.3 (q, J_(CF)=31.4, BAF: C_(m)), 129.3 and 128.5 (Ar,Ar′: C_(p)), 125.0 (q, J_(CF)=272.4, BAF: CF₃), 124.3 and 123.7 (Ar,Ar′: C_(m)), 117.9 (BAF: C_(p)), 29.2 and 28.9 (CHMe₂, C′HMe₂), 24.5,24.1, 23.0, and 22.5 (CHMeMe′, C′HMeMe′), 10.3 (PdMe). Anal. Calcd for(C₈₆H₉₀BClF₂₄N₄Pd₂): C, 54.52; H, 4.97; N, 2.96. Found: C, 54.97; H,4.72; N, 2.71.

Example 9

[0893] Alternatively, the products of Examples 7 and 8 have beensynthesized by stirring a 1:1 mixture of the appropriate PdMeCl compoundand NaBAF in Et₂O for ˜1 h. Removal of solvent yields the dimer +0.5equiv of Na⁺(OEt₂)₂BAF⁻. Washing the product mixture with hexane yieldsether-free NaBAF, which is insoluble in CH₂Cl₂. Addition of CH₂Cl₂ tothe product mixture and filtration of the solution yields salt-freedimer: ¹H NMR spectral data are identical with that reported above.

[0894] For a synthesis of CODPdMe₂, see: Rudler-Chauvin, M., and Rudler,H. J. Organomet. Chem. 1977, 134, 115-119.

Example 10 [(2,6-i-PrPh)₂DABMe₂]PdMe₂

[0895] A Schlenk flask containing a mixture of[(2,6-i-PrPh)₂DABMe₂]PdMeCl (2.00 g, 3.57 mmol) and 0.5 equiv of Me₂Mg(97.2 mg, 1.79 mmol) was cooled to −78° C., and the reaction mixture wasthen suspended in 165 mL of Et₂O. The reaction mixture was allowed towarm to room temperature and then stirred for 2 h, and the resultingbrown solution was then filtered twice. Cooling the solution to −30° C.yielded brown single crystals (474.9 mg, 24.6%, 2 crops): ¹H NMR (C₆D₆,400 MHz) δ7.2-7.1 (m, 6, H_(aryl)), 3.17 (septet, 4, J=6.92, CHMe₂),1.39 (d, 12, J=6.74, CHMeMe′), 1.20 (N═C(Me)—C(Me)═N), 1.03 (d, 12,J=6.89, CHMeMe′), 0.51 (s, 6, PdMe); ¹³C NMR (C₆D₆, 100 MHz) δ168.4(N═C—C═N), 143.4 (Ar: C_(ipso)), 138.0 (Ar: C_(o)), 126.5 (Ar: C_(p)),123.6 (Ar: C_(m)), 28.8 (CHMe₂), 23.6 and 23.5 (CHMeMe′), 19.5(N═C(Me)—C(Me)═N), −4.9 (J_(CH)=127.9, PdMe). Anal. Calcd for(C₃₀H₄₆N₂Pd): C, 66.59; H, 8.57; N, 5.18. Found: C, 66.77; H, 8.62; N,4.91.

Example 11 [(2,6-i-PrPh)₂DABH₂]PdMe₂

[0896] The synthesis of this compound in a manner analogous to Example10, using 3.77 mmol of ArN═C(H)—C(H)═NAr and 1.93 mmol of Me₂Mg yielded722.2 mg (37.4%) of a deep brown microcrystalline powder uponrecrystallization of the product from a hexane/toluene solvent mixture.

[0897] This compound was also synthesized by the following method: Amixture of Pd(acac)₂ (2.66 g, 8.72 mmol) and corresponding diimine (3.35g, 8.90 mmol) was suspended in 100 mL of Et₂O, stirred for 0.5 h at roomtemperature, and then cooled to −78° C. A solution of Me₂Mg (0.499 g,9.18 mmol) in 50 mL of Et₂O was then added via cannula to the coldreaction mixture. After stirring for 10 min at −78° C., the yellowsuspension was allowed to warm to room temperature and stirred for anadditional hour. A second equivalent of the diimine was then added tothe reaction mixture and stirring was continued for ˜4 days. The brownEt₂O solution was then filtered and the solvent was removed in vacuo toyield a yellow-brown foam. The product was then extracted with 75 mL ofhexane, and the resulting solution was filtered twice, concentrated, andcooled to −30° C. overnight to yield 1.43 g (32.0%) of brown powder: ¹HNMR (C₆D₆, 400 MHz) δ7.40 (S, 2, N═C(H)—C(H)═N), 7.12 (S, 6, H_(aryl)),3.39 (septet, 4, J=6.86, CHMe₂), 1.30 (d, 12, J=6.81, CHMeMe′), 1.07 (d,12, J=6.91, CHMeMe′), 0.77 (S, 6, PdMe); ¹³C NMR (C₆D₆, 100 MHz) δ159.9(J_(CH)=174.5, N═C(H)—C(H)═N), 145.7 (Ar: C_(ipso)), 138.9 (Ar: C_(o)),127.2 (Ar: C_(p)), 123.4 (Ar: C_(m)), 28.5 (CHMe₂), 24.4 and 22.8(CHMeMe′), −5.1 (J_(CH)=128.3, PdMe). Anal. Calcd for (C₂₈H₄₂N₂Pd): C,65.55, H, 8.25; N, 5.46. Found: C, 65.14; H, 8.12; N, 5.14.

Example 12 [(2,6-MePh)₂DABH₂]PdMe₂

[0898] This compound was synthesized in a manner similar to the secondprocedure of Example 11 (stirred for 5 h at rt) using 5.13 mmol of thecorresponding diimine and 2.57 mmol of Me₂Mg. After the reaction mixturewas filtered, removal of Et₂O in vacuo yielded 1.29 g (62.2%) of a deepbrown microcrystalline solid: ¹H NMR (C₆D₆, 100 MHz, 12° C.) δ6.98 (s,2, N═C(H)—C(H)═N), 6.95 (s, 6, H_(aryl)), 2.13 (s, 12, Ar: Me), 0.77 (s,6, PdMe); ¹³C NMR (C₆D₆, 400 MHz, 12° C.) δ160.8 (J_(CH)=174.6,N═C(H)—C(H)═N), 147.8 (Ar: C_(ipso)), 128.2 (Ar: C_(m)), 128.15 (Ar:C_(o)), 126.3 (Ar: C_(p)), 18.2 (Ar: Me), −5.5 (J_(CH)=127.6, Pd-Me).

Example 13 [(2,6-i-PrPh)₂DABH₂]NiMe₂

[0899] The synthesis of this compound has been reported (Svoboda, M.;tom Dieck, H. J. Organomet. Chem. 1980, 191, 321-328) and was modifiedas follows: A mixture of Ni(acac)₂ (1.89 g, 7.35 mmol) and thecorresponding diimine (2.83 g, 7.51 mmol) was suspended in 75 mL of Et₂Oand the suspension was stirred for 1 h at room temperature. Aftercooling the reaction mixture to −78° C., a solution of Me₂Mg (401 mg,7.37mmol) in 25 mL of Et₂O was added via cannula. The reaction mixturewas stirred for 1 h at −78° C. and then for 2 h at 0° C. to give ablue-green solution. After the solution was filtered, the Et₂O wasremoved in vacuo to give a blue-green brittle foam. The product was thendissolved in hexane and the resulting solution was filtered twice,concentrated, and then cooled to −30° C. to give 1.23 g (35.9% , onecrop) of small turquoise crystals.

Example 14 [(2,6-i-PrPh)₂DABMe₂]NiMe₂

[0900] The synthesis of this compound has been reported (Svoboda, M.;tom Dieck, H. J. Organomet. Chem. 1980, 191, 321-328) and wassynthesized according to the above modified procedure (Example 13) usingNi(acac)₂ (3.02 g, 11.75 mmol), the corresponding diimine (4.80 g, 11.85mmol) and Me₂Mg (640 mg, 11.77 mmol). A turquoise powder was isolated(620 mg, 10.7%).

Example 15 {[(2,6-MePh)₂DABMe₂]PdMe(MeCN)}BAF⁻

[0901] To a mixture of [(2,6-MePh)₂DABMe₂]PdMeCl (109.5 mg, 0.244 mmol)and NaBAF (216.0 mg, 0.244 mmol) were added 20 mL each of Et₂O andCH₂Cl₂ and 1 mL of CH₃CN. The reaction mixture was then stirred for 1.5h and then the NaCl was removed via filtration. Removal of the solventin vacuo yielded a yellow powder, which was washed with 50 mL of hexane.The product (269.6 mg, 83.8%) was then dried in vacuo: ¹H NMR (CD₂Cl₂,400 MHz) δ7.73 (s, 8, BAF: H_(o)), 7.57 (s, 4, BAF: H_(p)), 7.22-7.16(m, 6, H_(aryl)), 2.23 (s, 6, Ar: Me), 2.17 (s, 6, Ar′: Me), 2.16, 2.14,and 1.79 (s, 3 each, N═C(Me)—C′(Me)═N, NCMe), 0.38 (s, 3, PdMe); ¹³C NMR(CD₂Cl₂, 100 MHz) δ180.1 and 172.2 (N═C—C′═N), 162.1 (q, J_(BC)=49.9,BAF: C_(ipso)), 142.9 (Ar, Ar′: C_(o)), 135.2 (BAF: C_(o)) 129.3 (Ar:C_(m)), 129.2 (q, J_(CF)=30.6, BAF: C_(m)), 129.0 (Ar′: C_(m)), 128.4(Ar: C_(p)), 128.2 (Ar: C_(o)), 127.7 (Ar′: C_(p)), 127.4 (Ar′: C_(o)),125.0 (q, J_(CF)=272.4, BAF: CF₃), 121.8 (NCMe), 117.9 (BAF: C_(p)),20.2 and 19.2 (N═C(Me)—C′(Me)═N), 18.0 (Ar: Me), 17.9 (Ar′: Me), 5.1 and2.3 (NCMe, PdMe). Anal. Calcd for (C₅₅H₄₂BF₂₄N₃Pd): C, 50.12; H, 3.21;N, 3.19. Found: C, 50.13; H, 3.13, N, 2.99.

Example 16 {[(4-MePh)₂DABMe₂]PdMe (MeCN)}BAF⁻

[0902] Following the procedure of Example 15, a yellow powder wasisolated in 85% yield: ¹H NMR (CD₂Cl₂, 400 MHz) δ7.81 (s, 8, BAF:H_(o)), 7.73 (s, 4, BAF: H_(p)), 7.30 (d, 4, J=8.41, Ar, Ar′: H_(m)),6.89 (d, 2, J=8.26, Ar: H_(o)), 6.77 (d, 2, J=8.19, Ar′: H_(o)), 2.39(s, 6, Ar, Ar′: Me), 2.24, 2.17 and 1.93 (s, 3 each, N═C(Me)C—C′(Me)═N,NCMe)Pd-Me; ¹³C NMR (CD₂Cl₂, 100 MHz) δ180.7 and 171.6 (N═C—C′═N), 162.1(q, J_(BC)=49.8, BAF: C_(ipso)), 143.4 and 142.9 (Ar, Ar′: C_(ipso)),138.6 and 138.5 (Ar, Ar′: C_(p)), 135.2 (BAF: C_(o)), 130.6 and 130.4(Ar, Ar′: C_(m)), 129.3 (q, J_(CF)=31.6, BAF: C_(m)), 125.0 (q,J_(CF)=272.5, BAF: CF₃), 122.1 (NCMe), 121.0 and 120.9 (Ar, Ar′: C_(o)),117.9 (BAF: C_(p)), 21.5 (ArN═C(Me)), 21.1 (Ar, Ar′: Me), 19.7(ArN═C′(Me)), 6.2 and 3.0 (NCMe, PdMe). Anal. Calcd for(C₅₃H₃₈BF₂₄N₃Pd): C, 49.34; H, 2.97: N, 3.26. Found: C, 49.55; H, 2.93;N, 3.10.

Example 17 [(2,6-MePh)₂DABMe₂]PdMe (Et₂O)BAF⁻

[0903] A Schlenk flask containing a mixture of[(2,6-i-PrPh)₂DABMe₂]PdMe₂ (501 mg, 0.926 mmol) and H+(OEt₂)₂BAF⁻ (938mg, 0.926 mmol) was cooled to −78° C. Following the addition of 50 mL ofEt₂O, the solution was allowed to warm and stirred briefly (˜15 min) atroom temperature. The solution was then filtered and the solvent wasremoved in vacuo to give a pale orange powder (1.28 g, 94.5%), which wasstored at −30° C. under an inert atmosphere: ¹H NMR (CD₂Cl₂, 400 MHz,−60° C.) δ7.71 (s, 8, BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)), 7.4-7.0 (m,6, H_(aryl)), 3.18 (q, 4, J=7.10, O(CH₂CH₃)₂), 2.86 (septet, 2, J=6.65,CHMe₂), 2.80 (septet, 2, J=6.55, C′RMe₂), 2.18 and 2.15(N═C(Me)—C′(Me)═N), 1.34, 1.29, 1.14 and 1.13 (d, 6 each, J=6.4-6.7,CHMeMe′, C′HMeMe′), 1.06 (t, J=6.9, O(CH₂CH₃)₂), 0.33 (s, 3, PdMe); ¹³CNMR (CD₂Cl₂, 100 MHz, −60° C.) δ179.0 and 172.1 (N═C—C′═N), 161.4 (q,J_(BC)=49.7, BAF: C_(ipso)), 140.21 and 140.15 (Ar, Ar′: C_(ipso)),137.7 and 137.4 (Ar, Ar′: C_(o)), 134.4 (BAF: C_(p)), 128.3 (q,J_(CF)=31.3, BAF: C_(m)), 128.5 and 128.2 (Ar, Ar′: C_(p)), 124.2 (q,J_(CF)=272.4, BAF: CF₃), 117.3 (BAF: C_(p)), 71.5 (O(CH₂CH₃)₂), 28.7(CHMe₂), 28.4 (C′HMe₂), 23.7, 23.6, 23.1 and 22.6 (CHMeMe′, C′HMeMe′),21.5 and 20.7 (N═C(Me)—C′(Me)═N), 14.2 (O(CH₂CH₃)₂)₂, 8.6 (PdMe). Anal.Calcd for (C₆₅H₆₅BF₂₄N₂OPd): C, 53.35; H, 4.48; N, 1.91. Found: C,53.01; H, 4.35; N, 1.68.

Example 18 [(2,6-MePh)₂DABH₂]PdMe (Et₂O)BAF⁻

[0904] Following the procedure of Example 17, an orange powder wassynthesized in 94.3% yield and stored at −30° C.: ¹H NMR (CD₂Cl₂, 400MHz, −60° C.) δ8.23 and 8.20 (s, 1 each, N═C(H)—C′(H)═N), 7.72 (s, 8,BAF: H_(o)), 7.54 (s, 4, BAF: H_(p)), 7.40-7.27 (m, 6, H_(aryl)), 3.32(q, 4, J=6.90, O(CH₂CH₃)₂), 3.04 and 3.01 (septets, 2 each, J=6.9-7.1,CHMe₂ and C′HMe₂), 1.32, 1.318, 1.14 and 1.10 (d, 6 each, J=6.5-6.8,CHMeMe′ and C′HMeMe′), 1.21 (t, 6, J=6.93, O(CH₂CH₃)₂), 0.70 (s, 3,PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz, −60° C.) δ166.9 (J_(CH)=182.6, N═C(H)),161.5 (J_(BC)=49.7, BAF: C_(ipso)), 161.3 (J_(CH)=181.6, N═C′(H)), 143.0and 141.8 (Ar, Ar′: C_(ipso)), 138.7 and 137.8 (Ar, Ar′: C_(o)), 134.4(BAF: C_(o)), 129.1 and 128.8 (Ar, Ar′: C_(p)), 128.3 (J_(CF)=31.3, BAF:C_(m)), 124.0 and 123.9 (Ar, Ar′: C_(m)), 117.3 (BAF: C_(p)), 72.0(O(CH₂CH₃)₂), 28.5 and 28.4 (CHMe₂, C′HMe₂), 25.2, 24.1, 21.9 and 21.7(CHMeMe′, C′HMeMe′), 15.2 (O(CH₂CH₃)₂), 11.4 (J_(CH)=137.8, PdMe). Anal.Calcd for (C₆₃H₆₁BF₂₄N₂OPd): C, 52.72; H, 4.28; N, 1.95. Found: C,52.72; H, 4.26; N, 1.86.

Example 19 [(2,6-MePh)₂DABMe₂]NiMe (Et₂O)BAF⁻

[0905] Following the procedure of Example 17, a magenta powder wasisolated and stored at −30° C.: ¹H NMR (CD₂Cl₂, 400 MHz, −60° C.; A H₂Oadduct and free Et₂O were observed.) δ7.73 (s, 8, BAF: H_(o)), 7.55 (s,4, BAF: H_(p)), 7.4-7.2 (m, 6, H_(aryl)), 3.42 (s, 2, OH₂), 3.22 (q, 4,O(CH₂CH₃)₂), 3.14 and 3.11 (septets, 2 each, J=7.1, CHMe₂, C′HMe₂), 1.95and 1.78 (s, 3 each, N═C(Me)—C′(Me)═N), 1.42, 1.39, 1.18 and 1.11 (d, 6each, J=6.6-6.9, CHMeMe′ and C′HMeMe′), 0.93 (t, J=7.5, O(CH₂CH₃)₂),−0.26 (s ,3, NiMe); ¹³C NMR (CD₂Cl₂ 100 MHz, −58° C.) δ175.2 and 170.7(N═C—C′═N), 161.6 (q, J_(BC)=49.7, BAF: C_(ipso)), 141.2 (Ar: C_(ipso)),139.16 and 138.68 (Ar, Ar′: C_(o)), 136.8 (Ar′: C_(ipso)), 134.5 (BAF:C_(o)), 129.1 and 128.4 (Ar, Ar′: C_(p)), 128.5 (q, J_(CF)=32.4, BAF:C_(m)), 125.0 and 124.2 (Ar, Ar′: C_(m)), 124.3 (q, J_(CF)=272.5, BAF:CF₃), 117.4 (BAF: C_(p)), 66.0 (O(CH₂CH₃)₂), 29.1 (CHMe₂), 28.9(C′HMe₂), 23.51, 23.45, 23.03, and 22.95 (CHMeMe′, C′HMeMe′), 21.0 and19.2 (N═C(Me)—C′(Me)═N), 14.2 (OCH₂CH₃)₂), −0.86 (J_(CH)=131.8, NiMe).Anal. Calcd for (C₆₅H₆₅BF₂₄N₂NiO): C, 55.15; H, 4.63; N, 1.98. Found: C,54.74; H, 4.53; N, 2.05.

Example 20 [(2,6-MePh)₂DABH₂]NiMe(Et₂O)BAF⁻

[0906] Following the procedure of Example 17, a purple powder wasobtained and stored at −30° C.: ¹H NMR (CD₂Cl₂, 400 MHz, −80° C.; H₂Oand Et₂O adducts were observed in an 80:20 ratio, respectively.) δ8.31and 8.13 (s, 0.8 each, N═C(H)—C′(H)═N; H₂O Adduct), 8.18 and 8.00 (s,0.2 each, N═C(H)—C′(H)═N; Et₂O Adduct), 7.71 (s, 8 BAF: C_(o)), 7.53 (s,4, BAF: C_(p)), 7.5-7.0 (m, 6, H_(aryl)), 4.21 (s, 1.6, OH₂), 3.5-3.1(m, 8, O(CH₂CH₃)₂, CHMe₂, C′HMe₂), 1.38, 1.37, 1.16 and 1.08 (d, 4.8each, CHMeMe′, C′HMeMe′; H₂O Adduct; These peaks overlap with andobscure the CHMe₂ doublets of the Et₂O adduct.), 0.27 (s, 2.4, PdMe; H₂OAdduct), 0.12 (s, 0.6, PdMe: Et₂O Adduct).

Examples 21-23

[0907] The rate of exchange of free and bound ethylene was determined by¹H NMR line broadening experiments at −85° C. for complex (XI), see theTable below. The NMR instrument was a 400 MHz Varian® NMR spectrometer.Samples were prepared according to the following procedure: Thepalladium ether adducts {[(2,6-i-PrPh)₂DABMe₂]PdMe (OEt₂)}BAF,{[(2,6-i-PrPh)₂An]PdMe(OEt₂)}BAF, and{[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF were used as precursors to (XI), andwere weighed (˜15 mg) in a tared 5 mm dia. NMR tube in a nitrogen-filleddrybox. The tube was then capped with a septum and Parafilm® and cooledto −80° C. Dry, degassed CD₂Cl₂ (700 μL) was then added to the palladiumcomplex via gastight syringe, and the tube was shaken and warmed brieflyto give a homogeneous solution. After acquiring a −85° C. NMR spectrum,ethylene was added to the solution via gastight syringe and a second NMRspectrum was acquired at −85° C. The molarity of the BAF counterion wascalculated according to the moles of the ether adduct placed in the NMRtube. The molarity of (XI) and free ethylene were calculated using theBAF peaks as an internal standard. Line-widths (W) were measured athalf-height in units of Hz for the complexed ethylene signal (usually at5 to 4 ppm) and were corrected for line widths (W_(o)) in the absence ofexchange.

[0908] For (XI) the exchange rate was determined from the standardequation for the slow exchange approximation:

k=(W−W _(o))π/[=],

[0909] where [=] is the molar concentration of ethylene. Theseexperiments were repeated twice and an average value is reported below.Rate Constants for Ethylene Exchange^(a) k Ex. (XI) (L-M⁻¹s⁻¹) 21{[(2,6-i-PrPh)₂DABMe₂]PdMe(=)}BAF 45 22 {[(2,6-i-PrPh)₂An]PdMe(=)}BAF520 23 {[(2,6-i-PrPh)₂DABH₂]PdMe(=)}BAF 8100

Example 24

[0910] Anhydrous FeCl₂ (228 mg, 1.8 mmol) and (2,6-i-PrPh)₂DABAn (1.0 g,2.0 mmol) were combined as solids and dissolved in 40 ml of CH₂Cl₂. Themixture was stirred at 25° C. for 4 hr. The resulting green solution wasremoved from the unreacted FeCl₂ via filter cannula. The solvent wasremoved under reduced pressure resulting in a green solid (0.95 g, 84%yield).

[0911] A portion of the green solid (40 mg) was immediately transferredto another Schlenk flask and dissolved in 50 ml of toluene under 1 atmof ethylene. The solution was cooled to 0° C., and 6 ml of a 10% MAOsolution in toluene was added. The resulting purple solution was warmedto 25° C. and stirred for 11 hr. The polymerization was quenched and thepolymer precipitated by acetone. The resulting polymer was washed with6M HCl, water and acetone. Subsequent drying of the polymer resulted in60 mg of white polyethylene. ¹H NMR (CDCl₃, 200 MHz) δ1.25 (CH₂, CH)δ0.85 (m, CH₃).

Example 25 (2-t-BuPh)₂DABMe₂

[0912] A Schlenk tube was charged with 2-t-butylaniline (5.00 mL, 32.1mmol) and 2,3-butanedione (1.35 mL, 15.4 mmol). Methanol (10 mL) andformic acid (1 mL) were added and a yellow precipitate began to formalmost immediately upon stirring. The reaction mixture was allowed tostir overnight. The resulting yellow solid was collected via filtrationand dried under vacuum. The solid was dissolved in ether and dried overNa₂SO₄ for 2-3 h. The ether solution was filtered, condensed and placedinto the freezer (−30° C.). Yellow crystals were isolated via filtrationand dried under vacuum overnight (4.60 g, 85.7%): ¹H NMR (CDCl₃, 250MHz) δ7.41(dd, 2H, J=7.7, 1.5 Hz, H_(m)), 7.19 (td, 2H, J=7.5, 1.5 Hz,H_(m) or H_(p)), 7.07 (td, 2H, J=7.6, 1.6 Hz, H_(m) or H_(p)), 6.50 (dd,2H, J=7.7, 1.8 Hz, H_(o)), 2.19 (s, 6H, N═C(Me)—C(Me)═N), 1.34 (s, 18H,C(CH₃)₃).

Examples 26 and 27

[0913] General Polymerization Procedure for Examples 26 and 27: In thedrybox, a glass insert was loaded with [(η³—C₃H₅)Pd(μ-Cl)]₂ (11 mg, 0.03mmol), NaBAF (53 mg, 0.06 mmol), and an α-diimine ligand (0.06 mmol).The insert was cooled to −35° C. in the drybox freezer, 5 mL of C₆D₆ wasadded to the cold insert, and the insert was then capped and sealed.Outside of the drybox, the cold tube was placed under 6.9 MPa ofethylene and allowed to warm to RT as it was shaken mechanically for 18h. An aliquot of the solution was used to acquire a ¹H NMR spectrum. Theremaining portion was added to ˜20 mL of MeOH in order to precipitatethe polymer. The polyethylene was isolated and dried under vacuum

Example 26

[0914] α-Diimine was (2,6-i-PrPh)₂DABMe₂. Polyethylene (50 mg) wasisolated as a solid. ¹H NMR spectrum (C₆D₆) is consistent with theproduction of 1- and 2-butenes and branched polyethylene.

Example 27

[0915] α-Diimine was (2,6-i-PrPh)₂DABAn. Polyethylene (17 mg) wasisolated as a solid. ¹H NMR spectrum (C₆D₆) is consistent with theproduction of branched polyethylene.

Example 28 [(2,6-i-PrPh)₂DABH₂]NiBr₂

[0916] The corresponding diimine (980 mg, 2.61 mmol) was dissolved in 10mL of CH₂Cl₂ in a Schlenk tube under a N₂ atmosphere. This solution wasadded via cannula to a suspension of (DME)NiBr₂(DME=1,2-dimethoxyethane) (787 mg, 2.55 mmol) in CH₂Cl₂ (20 mL). Theresulting red/brown mixture was stirred for 20 hours. The solvent wasevaporated under reduced pressure resulting in a red/brown solid. Theproduct was washed with 3×10 mL of hexane and dried in vacuo. Theproduct was isolated as a red/brown powder (1.25 g, 82% yield).

Example 29 [(2,6-i-PrPh)₂DABMe₂]NiBr₂

[0917] Using a procedure similar to that of Example 28, 500 mg (1.62mmol) (DME)NiBr₂ and 687 mg (1.70 mmol) of the corresponding diiminewere combined. The product was isolated as an orange/brown powder (670mg, 67% yield).

Example 30 [(2,6-MePh)₂DABH₂]NiBr₂

[0918] Using a procedure similar to that of Example 28, 500 mg (1.62mmol) (DME)NiBr₂ and 448 mg (1.70 mmol) of the corresponding diiminewere combined. The product was isolated as a brown powder (622 mg, 80%yield).

Example 31 [(2,6-i-PrPh)₂DABAn]NiBr₂

[0919] Using a procedure similar to that of Example 28, 500 mg (1.62mmol) (DME)NiBr₂ and 850 mg (1.70 mmol) of the corresponding diiminewere combined. The product was isolated as a red powder (998 mg, 86%yield). Anal. Calcd. for C₃₆H₄₀N₂Br₂Ni: C, 60.12; H, 5.61; N, 3.89.Found C, 59.88; H, 5.20; N, 3.52.

Example 32 [(2,6-MePh)₂DABAn]NiBr₂

[0920] The corresponding diimine (1.92 g, 4.95 mmol) and (DME)NiBr₂ (1.5g, 4.86 mmol) were combined as solids in a flame dried Schlenk under anargon atmosphere. To this mixture 30 mL of CH₂Cl₂ was added giving anorange solution. The mixture was stirred for 18 hours resulting in ared/brown suspension. . The CH₂Cl₂ was removed via filter cannulaleaving a red/brown solid. The product was washed with 2×10 mL of CH₂Cl₂and dried under vacuum. The product was obtained as a red/brown powder(2.5 g, 83% yield).

Example 33 [(2,6-MePh)₂DABMe₂]NiBr₂

[0921] Using a procedure similar to that of Example 32, the titlecompound was made from 1.5 g (4.86 mmol) (DME)NiBr₂ and 1.45 g (4.95mmol) of the corresponding diimine. The product was obtained as a brownpowder (2.05 g, 81% yield).

Example 34 [(2,6-i-PrPh)₂DABMe₂]PdMeCl

[0922] (COD)PdMeCl (9.04 g, 34.1 mmol) was dissolved in 200 ml ofmethylene chloride. To this solution was added the corresponding diimine(13.79 g, 34.1 mmol). The resulting solution rapidly changed color fromyellow to orange-red. After stirring at room temperature for severalhours it was concentrated to form a saturated solution of the desiredproduct, and cooled to −40° C. overnight. An orange solid crystallizedfrom the solution, and was isolated by filtration, washed with petroleumether, and dried to afford 12.54 g of the title compound as an orangepowder. Second and third crops of crystals obtained from the motherliquor afforded an additional 3.22 g of product. Total yield=87%.

Examples 35-39

[0923] The following compounds were made by a method similar to thatused in Example 34. Example Compound 35 [(2,6-i-PrPh)₂DABH₂]PdMeCl 36[(2,6-i-PrPh)₂DABAn]PdMeCl 37 [(Ph)₂DABMe₂]PdMeCl 38[(2,6-EtPh)₂DABMe₂]PdMeCl 39 [(2,4,6-MePh)₂DABMe₂]PdMeCl

[0924] Note: The diethyl ether complexes described in Examples 41-46 areunstable in non-coordinating solvents such as methylene chloride andchloroform. They are characterized by ¹H NMR spectra recorded in CD₃CN;under these conditions the acetonitrile adduct of the Pd methyl cationis formed. Typically, less than a whole equivalent of free diethyletheris observed by ¹H NMR when [(R)₂DAB(R′)₂]PdMe(OEt₂)X is dissolved inCD₃CN. Therefore, it is believed the complexes designated as“{[(R)₂DAB(R′)₂]PdMe(OEt₂)}X” below are likely mixtures of{[(R)₂DAB(R′)₂]PdMe(OEt₂)}X and [(R)₂DAB(R′)₂]PdMeX, and in the lattercomplexes the X ligand (SbF₆, BF₄, or PF₆) is weakly coordinated topalladium. A formula of the type “{[(R)₂DAB(R′)₂]PdMe(OEt₂)}X” is a“formal” way of conveying the approximate overall composition of thiscompound, but may not accurately depict the exact coordination to themetal atom.

[0925] Listed below are the ¹³C NMR data for Example 36. ¹³C NMR dataTCB, 120C, 0.05M CrAcAc freq ppm intensity 46.5568 24.6005 1 cmp and/or1, 3 ccmcc 44.9321 3.42517 1, 3 cmc 40.8118 55.4341 2 pmp 40.3658145.916 1, 3 pmp 39.5693 18.458 methylenes from 2 cmp and/or 2 cmc38.7782 4.16118 38.6295 5.84037 38.2844 8.43098 38.1198 8.29802 37.83843.83966 37.5198 13.4977 37.2384 23.4819 37.1163 16.8339 36.7446 114.98336.0012 6.19217 35.7198 5.17495 34.2278 4.83958 32.9216 20.2781 3B₆ ⁺,3EOC 32.619 3.6086 32.4172 2.98497 32.1995 10.637 31.9765 42.254731.8809 143.871 30.4686 27.9974 30.3199 47.1951 30.0225 36.1409 29.7411102.51 29.311 4.83244 28.7111 117.354 28.2597 9.05515 27.1659 22.572527.0067 5.81855 26.1146 13.5772 24.5642 2.59695 ββB^(B) 22.6368 12.7262B₅ ⁺, 2EOC 20.1413 3.7815 2B₃ 19.7271 20.0959 1B₁ 17.5236 7.01554 endgroup 14.2528 3.03535 1B₃ 13.8812 12.3635 1B₄ ⁺, 1EOC

Example 40 {[(4-Me₂NPh)₂DABMe₂]PdMe (MeCN)}SbF₆.MeCN

[0926] A procedure analogous to that used in Example 54, using(4-Me₂NPh)₂DABMe₂ in place of (2-C₆H₄-^(t)Bu)₂DABMe₂, afforded{[(4-NMe₂Ph)₂DABMe₂]PdMe(MeCN)}SbF₆.MeCN as a purple solid (product wasnot recrystallized in this instance). ¹H NMR (CD₂Cl₂) δ6.96 (d, 2H,H_(aryl)), 6.75 (mult, 6H, H_(aryl)), 3.01 (s, 6H, NMe₂), 2.98 (s, 6H,NMe′₂), 2.30, 2.18, 2.03, 1.96 (s's, 3H each, N═CMe, N═CMe′, and freeand coordinated N≡CMe), 0.49 (s, 3H, Pd-Me).

Example 41 {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻

[0927] [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.84 g, 1.49 mmol) was suspended in50 mL of diethylether and the mixture cooled to −40° C. To this wasadded AgSbF₆ (0.52 g, 1.50 mmol). The reaction mixture was allowed towarm to room temperature, and stirred at room temperature for 90 min.The reaction mixture was then filtered, giving a pale yellow filtrateand a bright yellow precipitate. The yellow precipitate was extractedwith 4×20 mL 50/50 methylene chloride/diethyl ether. The filtrate andextracts were then combined with an additional 30 mL diethyl ether. Theresulting solution was then concentrated to half its original volume and100 mL of petroleum ether added. The resulting precipitate was filteredoff and dried, affording 1.04 g of the title compound as a yellow-orangepowder (83% yield). ¹H NMR (CD₃CN) δ7.30 (mult, 6H, H_(aryl)), 3.37 [q,free O(CH₂CH₃)₂], 3.05-2.90 (overlapping sept's, 4H, CHMe₂), 2.20 (s,3H, N═CMe), 2.19 (s, 3H, N═CMe′), 1.35-1.14 (overlapping d's, 24H,CHMe₂), 1.08 (t, free O(CH₂CH₃)₂], 0.28 (s, 3H, Pd-Me). This materialcontained 0.4 equiv of Et₂O per Pd, as determined by ¹H NMR integration.

Example 42 {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)_(n)}BF₄ ⁻

[0928] A procedure analogous to that used in Example 41, using AgBF₄ inplace of AgSbF₆, afforded the title compound as a mustard yellow powderin 61% yield. This material contained 0.3 equiv of Et₂O per Pd, asdetermined by ¹H NMR integration. ¹H NMR in CD₃CN was otherwiseidentical to that of the compound made in Example 41.

Example 43 {[(2,6-i-PrPh)₂DABMe₂]Pdme(Et₂O)_(n)}PF₆ ⁻

[0929] A procedure analogous to that used in Example 41, using AgPF₆ inplace of AgSbF₆, afforded the title compound as a yellow-orange powderin 72% yield. This material contained 0.4 equiv of Et₂O per Pd, asdetermined by ¹H NMR integration. ¹H NMR in CD₃CN was identical to thatof the compound of Example 41.

Example 44 {[(2,6-i-PrPh)₂DABH₂]PdMe(Et₂O)_(n)}SbF₆ ⁻

[0930] A procedure analogous to that used in Example 41, using[(2,6-i-PrPh)₂DABH₂]PdMeCl in place of [(2,6-i-PrPh)₂DABMe₂]PdMeCl,afforded the title compound in 71% yield. ¹H NMR (CD₃CN) δ8.30 (s, 2H,N═CH and N═CH′), 7.30 (s, 6H, H_(aryl)), 3.37 [q, free O(CH₂CH₃)₂], 3.15(br, 4H, CHMe₂), 1.40-1.10 (br, 24H, CHMe₂), 1.08 (t, free O(CH₂CH₃)₂],0.55 (s, 3H, Pd-Me). This material contained 0.5 equiv of Et₂O per Pd,as determined by ¹H NMR integration.

Example 45 {[(2,4,6-MePh)₂DABMe₂]PdMe(Et₂O)_(n)}SbF₆ ⁻

[0931] [(2,4,6-MePh)₂DABMe₂]PdMeCl (0.50 g, 1.05 mmol) was partiallydissolved in 40 mL 50/50 methylene chloride/diethylether. To thismixture at room temperature was added AgSbF₆ (0.36 g, 1.05 mmol). Theresulting reaction mixture was stirred at room temperature for 45 min.It was then filtered, and the filtrate concentrated in vacuo to affordan oily solid. The latter was washed with diethyl ether and dried toafford the title compound as a beige powder. ¹H NMR (CD₃CN) δ6.99 (s,4H, H_(aryl)), 3.38 [q, free O(CH₂CH₃)₂], 2.30-2.00 (overlapping s's,24H, N═CMe, N═CMe′ and aryl Me's), 1.08 (t, free O(CH₂CH₃)₂], 0.15 (s,3H, Pd-Me). This material contained 0.7 equiv of Et₂O per Pd, asdetermined by ¹H MR integration.

Example 46 {[(2,6-i-PrPh)₂DABAn]PdMe(Et₂O)_(n)}SbF₆ ⁻

[0932] A procedure analogous to that used in Example 41, using[(2,6-i-PrPh)₂DABAn]PdMeCl in place of [(2,6-i-PrPh)₂DABMe₂]PdMeCl,afforded the title compound in 92% yield. ¹H NMR (CD₃CN) δ8.22 (br t,2H, H_(aryl)), 7.60-7.42 (br mult, 8H, H_(aryl)), 6.93 (br d, 1H,H_(aryl)), 6.53 (br d, 1H, H_(aryl)) 3.38 [q, free O(CH₂CH₃)₂], 3.30 (brmult, 4H, CHMe₂), 1.36 (br d, 6H, CHMe₂), 1.32 (br d, 6H, CHMe₂), 1.08(t, free O(CH₂CH₃)₂], 1.02 (br d, 6H, CHMe₂), 0.92 (br d, 6H, CHMe₂),0.68 (s, 3H, Pd-Me). The amount of ether contained in the product couldnot be determined precisely by ¹H NMR integration, due to overlappingresonances.

Example 47 [(2,6-i-PrPh)₂DABMe₂]PdMe(OSO₂CF₃)

[0933] A procedure analogous to that used in Example 41, using AgOSO₂CF₃in place of AgSbF₆, afforded the title compound as a yellow-orangepowder. ¹H NMR in CD₃CN was identical to that of the title compound ofExample 41, but without free ether resonances.

Example 48 {[(2,6-i-PrPh)₂DABMe₂]PdMe (MeCN)}SbF₆ ⁻

[0934] [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.40 g, 0.71 mmol) was dissolved in15 mL acetonitrile to give an orange solution. To this was added AgSbF₆(0.25 g, 0.71 mmol) at room temperature. AgCl immediately precipitatedfrom the resulting bright yellow reaction mixture. The mixture wasstirred at room temperature for 3 h. It was then filtered and the AgClprecipitate extracted with 5 mL of acetonitrile. The combined filtrateand extract were concentrated to dryness affording a yellow solid. Thiswas recrystallized from methylene chloride/petroleum ether affording0.43 g of the title compound as a bright yellow powder (Yield=75%). ¹HNMR (CDCl₃) δ7.35-7.24 (mult, 6H, H_(aryl)), 2.91 (mult, 4H, CHMe₂),2.29 (s, 3H, N═CMe), 2.28 (s, 3H, N═CMe′), 1.81 (s, 3H, N≡CMe),1.37-1.19 (overlapping d's, 24H, CHMe's), 0.40 (s, 3H, Pd-Me). Thiscompound can also be prepared by addition of acetonitrile to{[(2,6-i-PrPh) ₂DABMe₂]PdMe (Et₂O)}SbF_(6.)

Example 49 {[(Ph)₂DABMe₂]PdMe(MeCN)}SbF₆ ⁻

[0935] A procedure analogous to that used in Example 48, using[(Ph)₂DABMe₂]PdMeCl in place of [(2,6-i-PrPh)₂DABMe₂]PdMeCl, affordedthe title compound as a yellow microcrystalline solid uponrecrystallization from methylene chloride/petroleum ether. This complexcrystallizes as the acetonitrile solvate from acetonitrile solution at−40° C. ¹H NMR of material recrystallized from methylenechloride/petroleum ether: (CDCl₃) δ7.46 (mult, 4H, H_(aryl)), 7.30 (t,2H, H_(aryl)), 7.12 (d, 2H, H_(aryl)), 7.00 (d, 2H, H_(aryl)), 2.31 (s,3H, N═CMe), 2.25 (s, 3H, N═CMe′), 1.93 (s, 3H, N≡CMe), 0.43 (s, 3H,Pd-Me).

Example 50 {[(2,6-EtPh)₂DABMe₂]PdMe (MeCN)}BAF⁻

[0936] [(2,6-EtPh)₂DABMe₂]PdMeCl (0.200 g, 0.396 mmol) was dissolved in10 mL of acetonitrile to give an orange solution. To this was addedNaBAF (0.350 g, 0.396 mmol). The reaction mixture turned bright yellowand NaCl precipitated. The reaction mixture was stirred at roomtemperature for 30 min and then filtered through a Celiteo® pad. TheCelite® pad was extracted with 5 mL of acetonitrile. The combinedfiltrate and extract was concentrated in vacuo to afford an orangesolid, recrystallization of which from methylene chloride/petroleumether at −40° C. afforded 0.403 g of the title compound as orangecrystals (Yield=74%). ¹H NMR (CDCl₃) δ7.68 (s, 8H, H_(ortho) of anion),7.51 (s, 4H, H_(para) of anion), 7.33-7.19 (mult, 6H, H_(aryl) ofcation), 2.56-2.33 (mult, 8H, CH₂CH₃), 2.11 (s, 3H, N═CMe), 2.09 (s, 3H,N═CMe′), 1.71 (s, 3H, N≡CMe), 1.27-1.22 (mult, 12H, CH₂CH₃), 0.41 (s,3H, Pd-Me).

Example 51 {[(2,6-EtPh)₂DABMe₂]PdMe(MeCN)}SbF₆ ⁻

[0937] A procedure analogous to that used in Example 50, using AgSbF₆ inplace of NaBAF, afforded the title compound as yellow crystals in 99%yield after recrystallization from methylene chloride/petroleum ether at−40° C.

Example 52 [(COD)PdMe(NCMe)]SbF₆ ⁻

[0938] To (COD)PdMeCl (1.25 g, 4.70 mmol) was added a solution ofacetonitrile (1.93 g, 47.0 mmol) in 20 mL methylene chloride. To thisclear solution was added AgSbF₆ (1.62 g, 4.70 mmol). A white solidimmediately precipitated. The reaction mixture was stirred at roomtemperature for 45 min, and then filtered. The yellow filtrate wasconcentrated to dryness, affording a yellow solid. This was washed withether and dried, affording 2.27 g of [(COD)Pdme(NCMe)]SbF₆ as a lightyellow powder (yield=95%). ¹H NMR (CD₂Cl₂) δ5.84 (mult, 2H, CH═CH), 5.42(mult, 2H, CH′═CH′), 2.65 (mult, 4H, CHH′), 2.51 (mult, 4H, CHH′), 2.37(s, 3H, NCMe), 1.18 (s, 3H, Pd-Me).

Example 53 [(COD) PdMe(NCMe)]BAF⁻

[0939] A procedure analogous to that used in Example 52, using NaBAF inplace of AgSbF₆, afforded the title compound as a light beige powder in96% yield.

Example 54 {[(2-t-BuPh)₂DABMe₂]PdMe(MeCN)}SbF₆ ⁻

[0940] To a suspension of (2-t-BuPh)₂DABMe₂ (0.138 g, 0.395 mmol) in 10mL of acetonitrile was added [(COD)PdMe(NCMe)]SbF₆ (0.200 g, 0.395mmol). The resulting yellow solution was stirred at room temperature for5 min. It was then extracted with 3×10 mL of petroleum ether. The yellowacetonitrile phase was concentrated to dryness, affording a brightyellow powder. Recrystallization from methylene chloride/petroleum etherat −40° C. afforded 180 mg of the title product as a bright yellowpowder (yield=61%). ¹H NMR (CD₂Cl₂) δ7.57 (dd, 2H, H_(aryl)), 7.32(mult, 4H, H_(aryl)), 6.88 (dd, 2H, H_(aryl)), 6.78 (dd, 2H, H_(aryl)),2.28 (s, 3H, N═CMe), 2.22 (s, 3H, N═CMe′), 1.78 (s, 3H, N≡CMe), 1.48 (s,18H, ^(t)Bu), 0.52 (s, 3H, Pd-Me).

Example 55 {[(Np)₂DABMe₂]PdMe (MeCN)}SbF₆ ⁻

[0941] A procedure analogous to that used in Example 54, using(Np)₂DABMe₂ in place of (2-t-BuPh)₂DABMe₂, afforded the title compoundas an orange powder in 52% yield after two recrystallizations frommethylene chloride/petroleum ether. ¹H NMR (CD₂Cl₂) δ8.20-7.19 (mult, 14H, H_(aromatic)), 2.36 (d, J=4.3 Hz, 3H, N═CMe), 2.22 (d, J=1.4 Hz, 3H,N═CMe′), 1.32 (s, 3H, NCMe), 0.22 (s, 3H, Pd-Me).

Example 56 {[(Ph₂CH)₂DABH₂]PdMe (MeCN)}SbF₆ ⁻

[0942] A procedure analogous to that used in Example 54, using(Ph₂CH)₂DABH₂ in place of (2-t-BuPh)₂DABMe₂, afforded the title compoundas a yellow microcrystalline solid. ¹H NMR (CDCl₃) δ7.69 (s, 1H, N═CH),7.65 (s, 1H, N═CH′), 7.44-7.08 (mult, 20H, H_(aryl)), 6.35 (2, 2H,CHPh₂), 1.89 (s, 3H, NCMe), 0.78 (s, 3H, Pd-Me).

Example 57 {[(2-PhPh)₂DABMe₂]PdMe (MeCN)}SbF₆ ⁻

[0943] A procedure analogous to that used in Example 54, using(2-PhPh)₂DABMe₂ in place of (2-t-BuPh)₂DABMe₂, afforded the titlecompound as a yellow-orange powder in 90% yield. Two isomers, due to cisor trans orientations of the two ortho phenyl groups on either side ofthe square plane, were observed by ¹H NMR. ¹H NMR (CD₂Cl₂) δ7.80-6.82(mult, 18H, H_(aryl)), 1.98, 1.96, 1.90, 1.83, 1.77, 1.73 (singlets, 9H,N═CMe, N═CMe′, NCMe for cis and trans isomers), 0.63, 0.61 (singlets,3H, Pd-Me for cis and trans isomers).

Example 58 {[(Ph)₂DAB (cyclo-CMe₂CH₂CMe₂-)]PdMe (MeCN) )BAF

[0944] To a solution of [(COD)PdMe(NCMe)]BAF⁻ (0.305 g, 0.269 mmol)dissolved in 15 mL of acetonitrile was addedN,N′-diphenyl-2,2′,4,4′-tetramethyl-cyclopentyldiazine (0.082 g, 0.269mmol). A gold colored solution formed rapidly and was stirred at roomtemperature for 20 min. The solution was then extracted with 4×5 mLpetroleum ether, and the acetonitrile phase concentrated to dryness toafford a yellow powder. This was recrystallized from methylenechloride/petroleum ether at −40° C. to afford 0.323 g (90%) of the titlecompound as a yellow-orange, crystalline solid. ¹H NMR (CDCl₃) δ7.71 (s,8H, H_(ortho) of anion), 7.54 (s, 4H, H_(para) of anion), 7.45-6.95(mult, 10H, H_(aryl) of cation), 1.99 (s, 2H, CH₂), 1.73 (s, 3H, NCMe),1.15 (s, 6H, Me₂), 1.09 (s, 6H, Me′₂), 0.48 (s, 3H, Pd-Me).

Example 59 {[(2,6-i-PrPh)₂DABMe₂]Pd(CH₂CH₂CH₂CO₂Me)}SbF₆ ⁻

[0945] Under a nitrogen atmosphere {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆⁻ (3.60 g, 4.30 mmol) was weighed into a round bottom flask containing amagnetic stirbar. To this was added a −40° C. solution of methylacrylate (1.85 g, 21.5 mmol) dissolved in 100 ml of methylene chloride.The resulting orange solution was stirred for 10 min, while beingallowed to warm to room temperature. The reaction mixture was thenconcentrated to dryness, affording a yellow-brown solid. The crudeproduct was extracted with methylene chloride, and the orange-redextract concentrated, layered with an equal volume of petroleum ether,and cooled to −40° C. This afforded 1.92 g of the title compound asyellow-orange crystals. An additional 1.39 g was obtained as a secondcrop from the mother liquor; total yield=91%. ¹H NMR (CD₂Cl₂) δ7.39-7.27(mult, 6H, H_(aryl)), 3.02 (s, 3H, OMe), 2.97 (sept, 4H, CHMe₂), 2.40(mult, 2H, CH₂), 2.24 (s, 3H, N═CMe), 2.22 (s, 3H, N═CMe′), 1.40-1.20(mult, 26H, CHMe₂ and CH₂′), 0.64 (mult, 2H, CH₂′′).

Example 60 {[(2,6-i-PrPh)₂DABH₂]Pd(CH₂CH₂CH₂CO₂Me)}SbF₆ ⁻

[0946] AgSbF₆ (0.168 g, 0.489 mmol) was added to a −40° C. solution of{[(2,6-i-PrPh)₂DABH₂]PdMeCl (0.260 g, 0.487 mmol) and methyl acrylate(0.210 g, 2.44 mmol) in 10 mL methylene chloride. The reaction mixturewas stirred for 1 h while warming to room temperature, and thenfiltered. The filtrate was concentrated in vacuo to give a saturatedsolution of the title compound, which was then layered with an equalvolume of petroleum ether and cooled to −40° C. Red-orange crystalsprecipitated from the solution. These were separated by filtration anddried, affording 0.271 g of the title compound (68% yield). ¹H NMR(CD₂Cl₂) δ8.38 (s, 1H, N═CH), 8.31 (s, 1H, N═CH′), 7.41-7.24 (mult, 6H,H_(aryl)), 3.16 (mult, 7H, OMe and CRMe₂), 2.48 (mult, 2H, CH₂), 1.65(t, 2H, CH₂′), 1.40-1.20 (mult, 24H, CHMe₂), 0.72 (mult, 2H, CH₂′′).

Example 61 {[(2,6-i-PrPh)₂DABMe₂]Pd (CH₂CH₂CH₂CO₂Me)}[B (C₆F₅)₃Cl]

[0947] [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.038 g, 0.067 mmol) and methylacrylate (0.028 g, 0.33 mmol) were dissolved in CD₂Cl₂. To this solutionwas added B(C₆F₅)₃ (0.036 g, 0.070 mmol). ¹H NMR of the resultingreaction mixture showed formation of the title compound.

Example 62

[0948] A 100 mL autoclave was charged with chloroform (50 mL),{[(2-t-BuPh)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.090 g, 0.12 mmol), and ethylene(2.1 MPa). The reaction mixture was stirred at 25° C. and 2.1 MPaethylene for 3 h. The ethylene pressure was then vented and volatilesremoved from the reaction mixture in vacuo to afford 2.695 g of branchedpolyethylene. The number average molecular weight (M_(n)), calculated by¹H NMR integration of aliphatic vs. olefinic resonances, was 1600. Thedegree of polymerization, DP, was calculated on the basis of the ¹H NMRspectrum to be 59; for a linear polymer this would result in 18methyl-ended branches per 1000 methylenes. However, based on the ¹H NMRspectrum the number of methyl-ended branches per 1000 methylenes wascalculated to be 154. Therefore, it may be concluded that this materialwas branched polyethylene. ¹H NMR (CDCl₃) δ5.38 (mult, vinyl H's), 1.95(mult, allylic methylenes), 1.62 (mult, allylic methyls), 1.24 (mult,non-allylic methylenes and methines), 0.85 (mult, non-allylic methyls).

Example 63

[0949] A suspension of {[(2-t-BuPh)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.015 g,0.02 mmol) in 5 mL FC-75 was agitated under 2.8 MPa of ethylene for 30min. The pressure was then increased to 4.1 MPa and maintained at thispressure for 3 h. During this time the reaction temperature variedbetween 25 and 40° C. A viscous oil was isolated from the reactionmixture by decanting off the FC-75 and dried in vacuo. The numberaverage molecular weight (M_(n)), calculated by ¹H NMR integration ofaliphatic vs. olefinic resonances, was 2600. DP for this material wascalculated on the basis of the ¹H NMR spectrum to be 95; for a linearpolymer this would result in 11 methyl-ended branches per 1000methylenes. However, based on the ¹H NMR spectrum the number ofmethyl-ended branches per 1000 methylenes was calculated to be 177.

Example 64

[0950] A 100 mL autoclave was charged with chloroform (55 mL),{[(2-PhPh)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.094 g, 0.12 mmol), and ethylene(2.1 MPa). The reaction mixture was stirred at 25° C. and 2.1 MPaethylene for 3 h. The ethylene pressure was then vented and volatilesremoved from the reaction mixture in vacuo to afford 2.27 g of a paleyellow oil. Mn was calculated on the basis of ¹H NMR integration ofaliphatic vs. olefinic resonances to be 200. The degree ofpolymerization, DP, was calculated on the basis of the ¹H NMR spectrumto be 7.2; for a linear polymer this would result in 200 methyl-endedbranches per 1000 methylenes. However, based on the ¹H NMR spectrum thenumber of methyl-ended branches per 1000 methylenes was calculated to be283.

Example 65

[0951] A suspension of [(2-PhPh)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.016 g, 0.02mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40min. During this time the reaction temperature varied between 23 and 41°C. A viscous oil (329 mg) was isolated from the reaction mixture bydecanting off the FC-75 and dried in vacuo. Mn was calculated on thebasis of ¹H NMR integration of aliphatic vs. olefinic resonances to be700. The degree of polymerization, DP, was calculated on the basis ofthe ¹H NMR spectrum to be 24.1; for a linear polymer this would resultin 45 methyl-ended branches per 1000 methylenes. However, based on the¹H NMR spectrum the number of methyl-ended branches per 1000 methyleneswas calculated to be 173.

Example 66

[0952] A 100 mL autoclave was charged with FC-75 (50 mL),{(Ph₂DABMe₂)PdMe(NCMe)}SbF6⁻ (0.076 g, 0.12 mmol) and ethylene (2.1MPa). The reaction mixture was stirred at 24° C. for 1.5 h. The ethylenepressure was then vented, and the FC-75 mixture removed from thereactor. A small amount of insoluble oil was isolated from the mixtureby decanting off the FC-75. The reactor was washed out with 2×50 mLCHCl₃, and the washings added to the oil. Volatiles removed from theresulting solution in vacuo to afford 144 mg of an oily solid. Mn wascalculated on the basis of ¹H NMR integration of aliphatic vs. olefinicresonances to be 400. The degree of polymerization, DP, was calculatedon the basis of the ¹H NMR spectrum to be 13.8; for a linear polymerthis would result in 83 methyl-ended branches per 1000 methylenes.However, based on the ¹H NMR spectrum the number of methyl-endedbranches per 1000 methylenes was calculated to be 288.

Example 67

[0953] A 100 mL autoclave was charged with chloroform (50 mL),{[(2,6-EtPh)₂DABMe₂]PdMe(NCMe)}BAF⁻ (0.165 g, 0.12 mmol), and ethylene(2.1 MPa). The reaction mixture was stirred under 2.1 MPa of ethylenefor 60 min; during this time the temperature inside the reactorincreased from 22 to 48° C. The ethylene pressure was then vented andvolatiles removed from the reaction mixture in vacuo to afford 15.95 gof a viscous oil. ¹H NMR of this material showed it to be branchedpolyethylene with 135 methyl-ended branches per 1000 methylenes. GPCanalysis in trichlorobenzene (vs. a linear polyethylene standard) gaveM_(n)=10,400, M_(w)=22,100.

Example 68

[0954] This was run identically to Example 67, but with{[(2,6-EtPh)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.090 g, 0.12 mmol) in place ofthe corresponding BAF salt. The temperature of the reaction increasedfrom 23 to 30° C. during the course of the reaction. 5.25 g of a viscousoil was isolated, ¹H NMR of which showed it to be branched polyethylenewith 119 methyl-ended branches per 1000 methylenes.

Example 69

[0955] A suspension of {[(Np)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.027 g, 0.02mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h;during this time the temperature inside the reactor varied between 25and 40° C. Two FC-75 insoluble fractions were isolated from the reactionmixture. One fraction, a non-viscous oil floating on top of the FC-75,was removed by pipette and shown by ¹H NMR to be branched ethyleneoligomers for which M_(n)=150 and with 504 methyl-ended branches per1000 methylenes. The other fraction was a viscous oil isolated byremoving FC-75 by pipette; it was shown by ¹H NMR to be polyethylene forwhich M_(n)=650 and with 240 methyl-ended branches per 1000 methylenes.

Example 70

[0956] A suspension of {[(Ph₂CH)₂DABH₂]PdMe (NCMe)}SbF₆ ⁻ (0.016 g, 0.02mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40min. During this time the reaction temperature varied between 23 and 41°C. A viscous oil (43 mg) was isolated from the reaction mixture bydecanting off the FC-75 and dried in vacuo. Mn was calculated on thebasis of ¹H NMR integration of aliphatic vs. olefinic resonances to beapproximately 2000. The degree of polymerization, DP, was calculated onthe basis of the ¹H NMR spectrum to be 73; for a linear polymer thiswould result in 14 methyl-ended branches per 1000 methylenes. However,based on the ¹H NMR spectrum the number of methyl-ended branches per1000 methylenes was calculated to be 377.

Example 71

[0957] A 100 mL autoclave was charged with FC-75 (50 mL), <{Ph₂DAB(cyclo—CMe₂CH₂CMe₂—)}PdMe(MeCN))BAF⁻ (0.160 g, 0.12 mmol) and ethylene (2.1MPa). The reaction mixture was stirred at 24-25° C. for 3.5 h. Theethylene pressure was then vented, and the cloudy FC-75 mixture removedfrom the reactor. The FC-75 mixture was extracted with chloroform, andthe chloroform extract concentrated to dryness affording 0.98 g of anoil. Mn was calculated on the basis of ¹H NMR integration of aliphaticvs. olefinic resonances to be 500. The degree of polymerization, DP, wascalculated on the basis of the ¹H NMR spectrum to be 19.5; for a linearpolymer this would result in 57 methyl-ended branches per 1000methylenes. However, based on the ¹H NMR spectrum the number ofmethyl-ended branches per 1000 methylenes was calculated to be 452.

Example 72

[0958] A 100 mL autoclave was charged with FC-75 (50 mL),{[(4-NMe₂Ph)₂DABMe₂]PdMe(MeCN)}SbF₆ ⁻ (MeCN) (0.091 g, 0.12 mmol) andethylene (2.1 MPa). The reaction mixture was stirred at 24° C. for 1.5h. The ethylene pressure was then vented, and the cloudy FC-75 mixtureremoved from the reactor. The FC-75 was extracted with 3×25 mL ofchloroform. The reactor was washed out with 3×40 mL CHCl₃, and thewashings added to the extracts. Volatiles removed from the resultingsolution in vacuo to afford 556 mg of an oil. Mn was calculated on thebasis of ¹H NMR integration of aliphatic vs. olefinic resonances to be200. The degree of polymerization, DP, was calculated on the basis ofthe ¹H NMR spectrum to be 8.4; for a linear polymer this would result in154 methyl-ended branches per 1000 methylenes. However, based on the ¹HNMR spectrum the number of methyl-ended branches per 1000 methylenes wascalculated to be 261.

Example 73

[0959] Under nitrogen, a 250 mL Schlenk flask was charged with 10.0 g ofthe monomer CH₂═CHCO₂CH₂CH₂(CF₂)_(n)CF₃ (avg n=9), 40 mL of methylenechloride, and a magnetic stirbar. To the rapidly stirred solution wasadded [(2,6-i-PrPh)₂DABMe₂]PdMe(OEt₂)}SbF₆ ⁻ (0.075 g, 0.089 mmol) insmall portions. The resulting yellow-orange solution was stirred under 1atm of ethylene for 18 h. The reaction mixture was then concentrated,and the viscous product extracted with ˜300 mL of petroleum ether. Theyellow filtrate was concentrated to dryness, and extracted a second timewith ˜150 mL petroleum ether. ˜500 mL of methanol was added to thefiltrate; the copolymer precipitated as an oil which adhered to thesides of the flask, and was isolated by decanting off the petroleumether/methanol mixture. The copolymer was dried, affording 1.33 g of aslightly viscous oil. Upon standing for several hours, an additional0.70 g of copolymer precipitated from the petroleum ether/methanolmixture. By ¹H NMR integration, it was determined that the acrylatecontent of this material was 4.2 mole %, and that it contained 26 esterand 87 methyl-ended branches per 1000 methylenes. GPC analysis intetrahydrofuran (vs. a PMMA standard) gave M_(n)=30,400, M_(w)=40,200.¹H NMR (CDCl₃) δ4.36 (t, CH₂CH₂CO2CH₂CH₂R_(f)), 2.45 (mult,CH₂CH₂CO2CH₂CH₂R_(f)), 2.31 (t, CH₂CH₂CO2CH₂CH₂R_(f)), 1.62 (mult,CH₂CH₂CO2CH₂CH₂R_(f)), 1.23 (mult, other methylenes and methines), 0.85(mult, methyls). ¹³C NMR gave branching per 1000 CH₂: Total methyls(91.3), Methyl (32.8), Ethyl(20), Propyl (2.2), Butyl (7.7), Amyl (2.2),≧Hex and end of chains (22.1). GPC analysis in THF gave M_(n)=30,400,M_(w)=40,200 vs. PMMA.

Example 74

[0960] A 100 mL autoclave was charged with [Pd(CH₃CH₂CN)₄](BF₄)₂ (0.058g, 0.12 mmol) and chloroform (40 mL). To this was added a solution of(2,6-i-PrPh)₂DABMe₂ (0.070 g, 0.17 mmol) dissolved in 10 mL ofchloroform under ethylene pressure (2.1 MPa). The pressure wasmaintained at 2.1 MPa for 1.5 h, during which time the temperatureinside the reactor increased from 22 to 35° C. The ethylene pressure wasthen vented and the reaction mixture removed from the reactor. Thereactor was washed with 3×50 mL of chloroform, the washings added to thereaction mixture, and volatiles removed from the resulting solution invacuo to afford 9.77 g of a viscous oil. ¹H NMR of this material showedit to be branched polyethylene with 96 methyl-ended branches per 1000methylenes.

Example 75

[0961] A 100 mL autoclave was charged with [Pd(CH₃CN)₄](BF₄)₂ (0.053 g,0.12 mmol) and chloroform (50 mL). To this was added a solution of(2,6-i-PrPh)₂DABMe₂ (0.070 g, 0.17 mmol) dissolved in 10 mL ofchloroform under ethylene pressure (2.1 MPa). The pressure wasmaintained at 2.1 MPa for 3.0 h, during which time the temperatureinside the reactor increased from 23 to 52° C. The ethylene pressure wasthen vented and the reaction mixture removed from the reactor. Thereactor was washed with 3'50 mL of chloroform, the washings added to thereaction mixture, and volatiles removed from the resulting solution invacuo to afford 25.98 g of a viscous oil. ¹H NMR of this material showedit to be branched polyethylene with 103 methyl-ended branches per 1000methylenes. GPC analysis in trichlorobenzene gave M_(n)=10,800,M_(w)=21,200 vs. linear polyethylene.

Example 76

[0962] A mixture of 20 mg (0.034 mmol) of [(2,6-i-PrPh)DABH₂]NiBr₂ and60 mL dry, deaerated toluene was magnetically-stirred under nitrogen ina 200-mL three-necked flask with a gas inlet tube, a thermometer, and agas exit tube which vented through a mineral oil bubbler. To thismixture, 0.75 mL (65 eq) of 3M poly(methylalumoxane) (PMAO) in toluenewas added via syringe. The resulting deep blue-black catalyst solutionwas stirred as ethylene was bubbled through at about 5 ml and 1 atm for2 hr. The temperature of the mixture rose to 60° C. in the first 15 minand then dropped to room temperature over the course of the reaction.

[0963] The product solution was worked up by blending with methanol; theresulting white polymer was washed with 2N HCl, water, and methanol toyield after drying (50° C./vacuum/nitrogen purge) 5.69 g (6000 catalystturnovers) of polyethylene which was easily-soluble in hotchlorobenzene. Differential scanning calorimetry exhibited a broadmelting point at 107° C. (67 J/g). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=22, 300;M_(w)=102, 000; M_(w)/M_(n)=4.56. ¹³C NMR analysis: branching per 1000CH₂: total Methyls (60), Methyl (41), Ethyl (5.8), Propyl (2.5), Butyl(2.4), Amyl (1.2), ≧Hexyl and end of chain (5); chemical shifts werereferenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). A film of polymer (pressed at 200°C.) was strong and could be stretched and drawn without elasticrecovery.

Example 77

[0964] In a Parr® 600-mL stirred autoclave under nitrogen was combined23 mg (0.039 mmol) of [(2,6-i-PrPh)DABH₂]NiBr₂, 60 mL of dry toluene,and 0.75 mL of poly(methylalumoxane) at 28° C. The mixture was stirred,flushed with ethylene, and pressurized to 414 kPa with ethylene. Thereaction was stirred at 414 kPa for 1 hr; the internal temperature roseto 31° C. over this time. After 1 hr, the ethylene was vented and 200 mLof methanol was added with stirring to the autoclave. The resultingpolymer slurry was filtered; the polymer adhering to the autoclave wallsand impeller was scraped off and added to the filtered polymer. Theproduct was washed with methanol and acetone and dried (80°C./vacuum/nitrogen purge) to yield 5.10 g (4700 catalyst turnovers) ofpolyethylene. Differential scanning calorimetry exhibited a meltingpoint at 127° C. (170 J/g). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=49,300;M_(w)=123, 000; M_(w)/M_(n)=2.51. Intrinsic viscosity (trichlorobenzene,135° C.): 1.925 dL/g. Absolute molecular weight averages corrected forbranching: M_(n)=47,400; M_(w)=134,000; M_(w)/M_(n)=2.83. ¹³C NMRanalysis; branching per 1000 CH₂: total Methyls (10.5), Methyl (8.4),Ethyl (0.9), Propyl (0), Butyl (0), >Butyl and end of chain (1.1);chemical shifts were referenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). A film of polymer (pressed at 200°C.) was strong and stiff and could be stretched and drawn withoutelastic recovery. This polyethylene is much more crystalline and linearthan the polymer of Example 76. This example shows that only a modestpressure increase from 1 atm to 414 kPa allows propagation tosuccessfully compete with rearrangement and isomerization of the polymerchain by this catalyst, thus giving a less-branched, more-crystallinepolyethylene.

Example 78

[0965] A mixture of 12 mg (0.020 mmol) of [(2,6-i-PrPh)DABH₂]NiBr₂ and40 mL dry, deaerated toluene was magnetically-stirred under nitrogen at15° C. in a 100-mL three-necked flask with an addition funnel, athermometer, and a nitrogen inlet tube which vented through a mineraloil bubbler. To this mixture, 0.5 mL of poly(methylalumoxane) in toluenewas added via syringe; the resulting burgundy catalyst solution wasstirred for 5 min and allowed to warm to room temperature. Into theaddition funnel was condensed (via a Dry Ice condenser on the top of thefunnel) 15 mL (about 10g) of cis-2-butene. The catalyst solution wasstirred as the cis-2-butene was added as a liquid all at once, and themixture was stirred for 16 hr. The product solution was treated with 1mL of methanol and was filtered through diatomaceous earth; rotaryevaporation yielded 0.35 g (300 catalyst turnovers) of a light yellowgrease, poly-2-butene. ¹³C NMR analysis; branching per 1000 CH₂: totalMethyls (365), Methyl (285), Ethyl (72), ≧Butyl and end of chain (8);chemical shifts were referenced to the solvent chloroform-d₁ (77 ppm).

[0966] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data CDCl₃, RT, 0.05M CnAcAc Freq ppm Intensity41.6071 11.2954 41.1471 13.7193 38.6816 3.55568 37.1805 7.07882 36.865733.8859 36.7366 35.1101 36.6196 33.8905 36.2645 12.1006 35.9094 13.327135.8004 11.8845 35.5785 4.20104 34.7351 24.9682 34.4325 39.3436 34.311459.2878 34.1177 125.698 33.9886 121.887 33.8837 120.233 33.5326 49.805833.004 132.842 32.7377 51.2221 32.657 55.6128 32.3705 18.1589 31.58769.27643 31.3818 16.409 31.0066 15.1861 30.0946 41.098 29.9736 42.800929.7072 106.314 29.3602 60.0884 29.2512 35.0694 29.114 26.6437 28.976929.1226 27.9358 3.57351 27.7501 3.56527 27.0682 14.6121 26.7333 81.076926.3257 14.4591 26.015 11.8399 25.3008 8.17451 25.0627 5.98833 22.48013.60955 2B₄ 22.3308 10.4951 2B₅+, EOC 19.6192 90.3272 1B₁ 19.4618154.354 1B₁ 19.3085 102.085 1B₁ 18.9937 34.7667 1B₁ 18.8525 38.7651 1B₁13.7721 11.2148 1B₄+, EOC, 1B₃ 11.0484 54.8771 1B₂ 10.4552 10.8437 1B₂10.1283 11.0735 1B₂ 9.99921 9.36226 1B₂

Example 79

[0967] A mixture of 10 mg (0.017 mmol) of [(2,6-i-PrPh)DABH₂]NiBr₂ and40 mL dry, deaerated toluene was magnetically-stirred under nitrogen at5° C. in a 100-mL three-necked flask with an addition funnel, athermometer, and a nitrogen inlet tube which vented through a mineraloil bubbler. To this mixture, 0.5 mL of 3M poly(methylalumoxane) intoluene was added via syringe; the resulting burgundy catalyst solutionwas stirred at 5° C. for 40 min. Into the addition funnel was condensed(via a Dry Ice condenser on the top of the funnel) 20 mL (about 15 g) of1-butene. The catalyst solution was stirred as the 1-butene was added asa liquid all at once. The reaction temperature rose to 50° C. over 30min and then dropped to room temperature as the mixture was stirred for4 hr. The product solution was treated with 1 mL of methanol and wasfiltered through diatomaceous earth; rotary evaporation yielded 6.17 g(1640 catalyst turnovers) of clear, tacky poly-1-butene rubber. Gelpermeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=64,700; M_(w)=115, 000; M_(w)/M_(n)=1.77. ¹³CNMR analysis; branching per 1000 CH₂: total Methyls (399), Methyl (86),Ethyl (272), ≧Butyl and end of chain (41); chemical shifts werereferenced to the solvent chloroform-d₁ (77 ppm). This exampledemonstrates the polymerization of an alpha-olefin and shows thedifferences in branching between a polymer derived from a 1-olefin (thisexample) and a polymer derived from a 2-olefin (Example 78). Thisdifference shows that the internal olefin of Example 78 is not firstisomerized to an alpha-olefin before polymerizing; thus this catalyst istruly able to polymerize internal olefins.

[0968] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data CDCl₃, RT, 0.05M CrAcAc Freq ppm Intensity43.8708 6.42901 41.5304 11.1597 41.0825 16.1036 38.7623 103.647 38.124750.3288 37.3338 24.6017 36.8173 30.0925 35.756 55.378 35.0337 22.356334.1419 64.8431 33.8514 55.3508 33.4116 90.2438 33.0645 154.939 32.709451.3245 32.431 23.0013 3B₅ 30.946 12.8866 3B₆+ 30.1551 26.1216 29.751654.6262 29.4248 40.7879 27.6008 8.64277 27.2417 20.1564 27.1207 21.973526.7777 45.0824 26.0755 66.0697 25.6599 77.1097 24.3807 8.9175 23.480932.0249 2B₄, 2B₅+, 2EOC 22.8393 8.06774 22.1372 16.4732 19.4981 57.70031B₁ 19.3609 70.588 1B₁ 15.132 17.2402 1B₄+ 13.8448 7.9343 1B₄+ 12.250927.8653 12.037 27.0118 11.0766 6.61931 1B₂ 10.2938 98.0101 1B₂ 10.1364104.811 1B₂

Example 80

[0969] A 22-mg (0.037-mmol) sample of [(2,6-i-PrPh)DABH₂]NiBr₂ wasintroduced into a 600-mL stirred Parr® autoclave under nitrogen. Theautoclave was sealed and 75 mL of dry, deaerated toluene was introducedinto the autoclave via gas tight syringe through a port on the autoclavehead. Then 0.6 mL of 3M poly(methylalumoxane) was added via syringe andstirring was begun. The autoclave was pressurized with propylene to 414kPa and stirred with continuous propylene feed. There was no externalcooling. The internal temperature quickly rose to 330C upon initialpropylene addition but gradually dropped back to 24° C. over the courseof the polymerization. After about 7 min, the propylene feed was shutoff and stirring was continued; over a total polymerization time of 1.1hr, the pressure dropped from 448 kPa to 358 kPa. The propylene wasvented and the product, a thin, honeycolored solution, was rotaryevaporated to yield 1.65 g of a very thick, brown semi-solid. This wasdissolved in chloroform and filtered through diatomaceous earth;concentration yielded 1.3 g (835 catalyst turnovers) of tacky, yellowpolypropylene rubber. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polypropyleneusing universal calibration theory): M_(n)=7,940; M_(w)=93,500;M_(w)/M_(n)=11.78.

Example 81

[0970] A mixture of 34 mg (0.057 mmol) of [(2,6-i-PrPh)DABH₂]NiBr₂ and20 mL dry, deaerated toluene was magnetically-stirred under nitrogen at5° C. in a 100-mL three-necked flask with a thermometer and a nitrogeninlet tube which vented through a mineral oil bubbler. To this mixture,0.7 mL of 3M poly(methylalumoxane) in toluene was added via syringe andthe resulting deep blue-black solution was stirred for 30 min at 5° C.To this catalyst solution was added 35 mL of dry, deaeratedcyclopentene, and the mixture was stirred and allowed to warm to roomtemperature over 23 hr. The blue-black mixture was filtered throughalumina to remove dark blue-green solids (oxidized aluminum compoundsfrom PMAO); the filtrate was rotary evaporated to yield 1.2 g (310catalyst turnovers) of clear liquid cyclopentene oligomers.

Example 82

[0971] A 20-mg (0.032 mmol) sample of [(2,6-i-PrPh)DABMe₂]NiBr₂ wasplaced in Parr® 600-mL stirred autoclave under nitrogen. The autoclavewas sealed and 100 mL of dry, deaerated toluene and 0.6 mL of 3Mpoly(methylalumoxane) were injected into the autoclave through the headport, and mixture was stirred under nitrogen at 20° C. for 50 min. Theautoclave body was immersed in a flowing water bath and the autoclavewas then pressurized with ethylene to 2.8 MPa with stirring as theinternal temperature rose to 53° C. The autoclave was stirred at 2.8 MPa(continuous ethylene feed) for 10 min as the temperature dropped to 29°C., and the ethylene was then vented. The mixture stood at 1 atm for 10min; vacuum was applied to the autoclave for a few minutes and then theautoclave was opened.

[0972] The product was a stiff, swollen polymer mass which was scrapedout, cut up, and fed in portions to 500 mL methanol in a blender. Thepolymer was then boiled with a mixture of methanol (200 mL) andtrifluoroacetic acid (10 mL), and finally dried under high vacuumovernight to yield 16.8 g (18,700 catalyst turnovers) of polyethylene.The polymer was. somewhat heterogeneous with respect to crystallinity,as can be seen from the differential scanning calorimetry data below;amorphous and crystalline pieces of polymer could be picked out of theproduct. Crystalline polyethylene was found in the interior of thepolymer mass; amorphous polyethylene was on the outside. The crystallinepolyethylene was formed initially when the ethylene had good access tothe catalyst; as the polymer formed limited mass transfer, the catalystbecame ethylene-starved and began to make amorphous polymer.Differential scanning calorimetry: (crystalline piece of polymer): mp:130° C. (150J/g); (amorphous piece of polymer): −48° C. (Tg); mp: 42° C.(3J/g), 96° C. (11J/g). Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=163,000; M_(w)=534,000; M_(w/M)_(n)=3.27. This example demonstrates the effect of ethylene masstransfer on the polymerization and shows that the same catalyst can makeboth amorphous and crystalline polyethylene. The bulk of the polymer wascrystalline: a film pressed at 200° C. was tough and stiff.

Example 83

[0973] A 29-mg (0.047 mmol) sample of [(2,6-i-PrPh)DABMe₂]NiBr₂ wasplaced in Parr® 600-mL stirred autoclave under nitrogen. The autoclavewas sealed and 100 mL of dry, deaerated toluene and 0.85 mL of 3Mpoly(methylalumoxane) were injected into the autoclave through the headport. The mixture was stirred under nitrogen at 23° C. for 30 min. Theautoclave body was immersed in a flowing water bath and the autoclavewas pressurized with ethylene to 620 kPa with stirring. The internaltemperature peaked at 38° C. within 2 min. The autoclave was stirred at620 kPa (continuous ethylene feed) for 5 min as the temperature droppedto 32° C. The ethylene was then vented, the regulator was readjusted,and the autoclave was pressurized to 34.5 kPa (gauge) and stirred for 20min (continuous ethylene feed) as the internal temperature dropped to22° C. In the middle of this 20 min period, the ethylene feed wastemporarily shut off for 1 min, during which time the autoclave pressuredropped from 34.5 kPa (gauge) to 13.8 kPa; the pressure was thenrestored to 34.5 kPa. After stirring 20 min at 34.5 kPa, the autoclavewas once again pressurized to 620 kPa for 5 min; the internaltemperature rose from 22° C. to 34° C. The ethylene feed was shut offfor about 30 sec before venting; the autoclave pressure dropped to about586 kPa.

[0974] The ethylene was vented; the product was a dark, thick liquid.Methanol (200 mL) was added to the autoclave and the mixture was stirredfor 2 hr. The polymer, swollen with toluene, had balled up on thestirrer, and the walls and bottom of the autoclave were coated withwhite, fibrous rubbery polymer. The polymer was scraped out, cut up, andblended with methanol in a blender and then stirred with fresh boilingmethanol for 1 hr. The white rubber was dried under high vacuum for 3days to yield 9.6 g (7270 catalyst turnovers) of rubbery polyethylene.¹H NMR analysis (CDCl₃): 95 methyl carbons per 1000 methylene carbons.

[0975] Differential scanning calorimetry: −51° C. (Tg); mp: 39.5° C.(4J/g); mp: 76.4° C. (7J/g). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=223,000;M_(w)=487,000; M_(w)/M_(n)=2.19.

[0976] The polyethylene of Example 83 could be cast from hotchlorobenzene or pressed at 200° C. to give a strong, stretchy, hazy,transparent film with good recovery. It was not easilychloroform-soluble. This example demonstrates the use of the catalyst'sability (see Example 82) to make both amorphous and crystalline polymer,and to make both types of polymer within the same polymer chain due tothe catalyst's low propensity to chain transfer. With crystalline blocks(due to higher ethylene pressure) on both ends and an amorphous region(due to lower- pressure, mass transfer-limited polymerization) in thecenter of each chain, this polymer is a thermoplastic elastomer.

Example 84

[0977] A Schlenk flask containing 147 mg (0.100 mmol) of{[(2,6-i-PrPh)DABMe₂]PdMe(OEt₂)}BAF⁻ was cooled to −78° C., evacuated,and placed under an ethylene atmosphere. Methylene chloride (100 ml) wasadded to the flask and the solution was then allowed to warm to roomtemperature and stirred. The reaction vessel was warm during the firstseveral hours of mixing and the solution became viscous. After beingstirred for 17.4 h, the reaction mixture was added to ˜600 mL of MeOH inorder to precipitate the polymer. Next, the MeOH was decanted off of thesticky polymer, which was then dissolved in ˜600 mL of petroleum ether.After being filtered through plugs of neutral alumina and silica gel,the solution appeared clear and almost colorless. The solvent was thenremoved and the viscous oil (45.31 g) was dried in vacuo for severaldays: ¹H NMR (CDCl₃, 400 MHz) δ1.24 (CH₂, CH), 0.82 (m, CH₃); Branching:˜128 CH₃ per 1000 CH₂; DSC: Tg=−67.7° C. GPC: M_(n)=29,000;M_(w)=112,000.

Example 85

[0978] Following the procedure of Example 84{[(2,6-i-PrPh)DABMe₂]PdMe(OEt₂)}BAF⁻ (164 mg, 0.112 mmol) catalyzed thepolymerization of ethylene for 24 h in 50 mL of CH₂Cl₂ to give 30.16 gof polymer as a viscous oil. ¹H NMR (C₆D₆) δ1.41 (CH₂, CH), 0.94 (CH₃);Branching: ˜115 CH₃ per 1000 CH₂; GPC Analysis (THF, PMMA standards, RIDetector): M_(w)=262,000; M_(n)=121,000; PDI=2.2; DSC: T_(g)=−66.8° C.

Example 86

[0979] The procedure of Example 84 was followed using 144 mg (0.100mmol) of {[(2,6-i-PrPh)DABH₂]PdMe(OEt₂)}BAF⁻ in 50 mL of CH₂Cl₂ and a 24h reaction time. Polymer (9.68 g) was obtained as a free-flowing oil. ¹HNMR (CDCl₃, 400 MHz) δ5.36 (m, RHC═CHR′), 5.08 (br s, RR′C═CHR″), 4.67(br s, H₂C═CRR′), 1.98 (m, allylic H), 1.26 (CH₂, CH), 0.83 (m, CH₃);Branching: ˜149 CH₃ per 1000 CH₂; DSC: T_(g)=−84.6° C.

Example 87

[0980] A 30-mg (0.042-mmol) sample of [(2,6-i-PrPh) DABAn]NiBr₂ wasplaced in Parr® 600-mL stirred autoclave under nitrogen. The autoclavewas sealed and 150 mL of dry toluene and 0.6 mL of 3Mpolymethylalumoxane were injected into the autoclave through the headport. The autoclave body was immersed in a flowing water bath and themixture was stirred under nitrogen at 20° C. for 1 hr. The autoclave wasthen pressurized with ethylene to 1.31 MPa with stirring for 5 min asthe internal temperature peaked at 30° C. The ethylene was then ventedto 41.4 kPa (gauge) and the mixture was stirred and fed ethylene at 41.4kPa for 1.5 hr as the internal temperature dropped to 19° C. At the endof this time, the autoclave was again pressurized to 1.34 MPa andstirred for 7 min as the internal temperature rose to 35° C.

[0981] The ethylene was vented and the autoclave was briefly evacuated;the product was a stiff, solvent-swollen gel. The polymer was cut up,blended with 500 mL methanol in a blender, and then stirred overnightwith 500 mL methanol containing 10 mL of 6N HCl. The stirred suspensionin methanol/HCl was then boiled for 4 hr, filtered, and dried under highvacuum overnight to yield 26.1 g (22,300 catalyst turnovers) ofpolyethylene. Differential scanning calorimetry: −49° C. (Tg); mp: 116°C. (42J/g). The melting transition was very broad and appeared to beginaround room temperature. Although the melting point temperature ishigher in this Example than in Example 76, the area under the meltingendotherm is less in this example, implying that the polymer of thisExample is less crystalline overall, but the crystallites that do existare more ordered. This indicates that the desired block structure wasobtained. Gel permeation chromatography (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=123,000; M_(w)=601,000;M_(w)/M_(n)=4.87. The polyethylene of this example could be pressed at200° C. to give a strong, tough, stretchy, hazy film with partialelastic recovery. When the stretched film was plunged into boilingwater, it completely relaxed to its original dimensions.

Example 88

[0982] A 6.7-mg (0.011-mmol) sample of [(2,6-i-PrPh)DABMe₂]NiBr₂ wasmagnetically-stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene as 0.3 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture was stirred at 23° C. for 40 min togive a deep blue-green solution of catalyst. Dry, deaerated cyclopentene(10 mL) was injected and the mixture was stirred for 5 min. The flaskwas then pressurized with ethylene at 20.7 MPa and stirred for 22 hr.The resulting viscous solution was poured into a stirred mixture of 200mL methanol and 10 mL 6N HCl. The methanol was decanted off and replacedwith fresh methanol, and the polymer was stirred in boiling methanol for3 hr. The tough, stretchy rubber was pressed between paper towels anddried under vacuum to yield 1.0 g of poly[ethylene/cyclopentene]. By ¹HNMR analysis(CDCl₃): 100 methyl carbons per 1000 methylene carbons.Comparison of the peaks attributable to cyclopentene (0.65 ppm and 1.75ppm) with the standard polyethylene peaks (0.9 ppm and 1.3 ppm)indicates about a 10 mol % cyclopentene incorporation. This polymeryield and composition represent about 2900 catalyst turnovers.Differential scanning calorimetry: −44° C. (Tg). Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n)=122,000; M_(w)=241,000; M_(w)/M_(n)=1.97.

[0983] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120C, 0.05M CrAcAc Freq ppm Intensity50.9168 5.96663 46.3865 3.27366 1 cme and/or 1,3 ccmcc 40.7527 40.5963 2eme 40.567 41.9953 1,3 eme 40.3336 45.8477 1,3 eme 37.1985 60.100336.6998 41.2041 36.0579 11.2879 35.607 25.169 34.4771 19.0834 34.084522.8886 33.1243 20.1138 32.8962 27.6778 31.8406 75.2391 30.0263 76.275529.6921 170.41 28.9494 18.8754 28.647 25.8032 27.4588 22.2397 27.108648.0806 24.3236 3.31441 22.5783 4.64411 2B₅+, 2 EOC 19.6712 43.1867 1B₁17.5546 1.41279 end group 14.3399 1.74854 1B₃ 13.8518 5.88699 1B₄+, 1EOC10.9182 2.17785 2B₁

Example 89

[0984] A 7.5-mg (0.013-mmol) sample of [(2,6-t-BuPh)DABMe₂]NiBr₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 40 mLof dry, deaerated toluene as 0.5 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture was stirred at 23° C. for 1 hr to givea deep blue-green solution of catalyst. The flask was pressurized withethylene at 20.7 kPa (gauge) and stirred for 20 hr. The solution, whichhad become a reddish-brown suspension, was poured into a stirred mixtureof 200 mL methanol and 10 mL 6N HCl and was stirred at reflux for 1 hr.The methanol was decanted off and replaced with fresh methanol, and thewhite polymer was stirred in boiling methanol for 1 hr. The stiff,stretchy rubber was pressed between paper towels and then dried undervacuum to yield 1.25 g (3380 catalyst turnovers) of polyethylene. ¹H-1NMR analysis (C₆D₆): 63 methyl carbons per 1000 methylene carbons.Differential scanning calorimetry: −34° C. (Tg); mp: 44° C. (31J/g); mp:101° C. (23J/g).

Example 90

[0985] A 5.5 mg (0.0066 mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ was allowed to stand at roomtemperature in air for 24 hr. A 100-mL three-neck flask with a magneticstirrer and a gas inlet dip tube was charged with 40 mL of reagentmethylene chloride and ethylene gas was bubbled through with stirring tosaturate the solvent with ethylene. The sample of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ was then rinsed into the flaskwith 5 mL of methylene chloride and ethylene was bubbled through withstirring for 5 hr. The clear yellow solution was rotary evaporated toyield 0.20 g (1080 catalyst turnovers) of a thick yellow liquidpolyethylene.

Example 91

[0986] A 600-mL stirred Parr® autoclave was sealed and flushed withnitrogen, and 100 mL of dry, deaerated toluene was introduced into theautoclave via gas tight syringe through a port on the autoclave head.The autoclave was purged with propylene gas to saturate the solvent withpropylene. Then 45 mg (0.054 mmol) of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ was introduced into theautoclave in the following manner: a 2.5-mL gas tight syringe with asyringe valve was loaded with 45 mg of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ under nitrogen in a glove box; then 1-2 mL of dry,deaerated methylene chloride was drawn up into the syringe and thecontents were quickly injected into the autoclave through a head port.This method avoids having the catalyst in solution with no stabilizingligands.

[0987] The autoclave was pressurized with propylene to 414 MPa andstirred for 2.5 hr, starting with continuous propylene feed. Theautoclave was cooled in a running tap water bath at 22° C. The internaltemperature quickly rose to 30° C. upon initial propylene addition butsoon dropped back to 22° C. After 0.5 hr, the propylene feed was shutoff and stirring was continued. Over 2 hr, the pressure dropped from41.4 MPa to 38.6 MPa. The propylene was then vented. The product was athin, honey-colored solution. Rotary evaporation yielded 2.3 g (1010catalyst turnovers) of very thick, dark-brown liquid polypropylene whichwas almost elastomeric when cool. Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolypropylene using universal calibration theory): M_(n)=8,300;M_(w)=15,300; M_(w)/M_(n)=1.84. ¹³C NMR analysis; branching per 1000CH₂: total Methyls (545), Propyl (1.3), ≧Butyl and end of chain (9.2);chemical shifts. The polymer exhibited a glass transition temperature of−44° C. by differential scanning calorimetry.

[0988] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data CDCl₃, RT, 0.05M CrAcAc Freq ppm Intensity46.4978 13.2699 Methylenes 45.8683 11.9947 Methylenes 45.3639 10.959Methylenes 45.1783 11.3339 Methylenes 44.5568 8.41708 Methylenes 44.43987.69019 Methylenes 44.3026 6.29108 Methylenes 44.1372 6.73541 Methylenes43.5036 5.49837 Methylenes 42.4262 5.03113 Methylenes 41.6918 3.72552Methylenes 39.1537 4.23147 Methines and Methylenes 38.7179 25.2596Methines and Methylenes 37.8664 10.0979 Methines and Methylenes 37.672714.3755 Methines and Methylenes 37.0755 17.623 Methines and Methylenes36.781 42.0719 Methines and Methylenes 36.559 10.0773 Methines andMethylenes 34.5495 5.34388 Methines and Methylenes 34.3195 7.48969Methines and Methylenes 33.5488 12.6148 Methines and Methylenes 33.35120.5271 Methines and Methylenes 32.7982 4.10612 Methines and Methylenes32.4108 22.781 Methines and Methylenes 31.8701 5.90488 Methines andMethylenes 31.5957 10.6988 Methines and Methylenes 29.8364 44.4935Methines and Methylenes 29.7072 103.844 Methines and Methylenes 29.3925152.645 Methines and Methylenes 29.0293 6.71341 Methines and Methylenes27.6089 38.7993 Methines and Methylenes 27.4193 10.3543 Methines andMethylenes 27.0763 66.8261 Methines and Methylenes 26.9552 92.859Methines and Methylenes 26.7615 55.7233 Methines and Methylenes 26.366120.1674 Methines and Methylenes 24.8529 16.9056 Methine Carbon of XXVIII23.1217 12.5439 Methine carbons of XXVIII and XXIX, 2B₄+, EOC 22.677913.0147 Methine carbons of XXVIII and XXIX, 2B₄+, EOC 22.5245 9.16236Methine carbons of XXVIII and XXIX, 2B₄+, EOC 22.3389 77.3342 Methinecarbons of XXVIII and XXIX, 2B₄+, EOC 21.9757 9.85242 Methine carbons ofXXVIII and XXIX, 2B₄+, EOC 21.1405 10.0445 Methyls 20.4182 8.49663Methyls 19.9743 25.8085 Methyls 19.825 31.4787 Methyls 19.3811 44.9986Methyls 19.1995 31.3058 Methyls 13.8569 6.37761 Methyls 13.8004 7.67242Methyls 137.452 22.0529 Methyls 128.675 44.6993 Methyls 127.88 43.8939Methyls 124.959 22.4025 Methyls 122.989 3.3312 Methyls

Example 92

[0989] A 600-mL stirred Parr® autoclave was sealed, flushed withnitrogen, and heated to 60° C. in a water bath. Fifty mL (48 g; 0.56mol) of dry, deaerated methyl acrylate was introduced into the autoclavevia gas tight syringe through a port on the autoclave head and ethylenegas was passed through the autoclave at a low rate to saturate thesolvent with ethylene before catalyst addition. Then 60 mg (0.07 mmol)of {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ was introduced into theautoclave in the following manner: a 2.5-mL gas tight syringe with asyringe valve was loaded with 60 mg of{[(2,6-i-PrPh)₂DADMe₂]PdMe(Et₂O)}SbF₆ ⁻ under nitrogen in a glove box;then 1 mL of dry, deaerated methylene chloride was drawn up into thesyringe and the contents were quickly injected into the autoclavethrough a head port. This method avoids having the catalyst in solutionwith no stabilizing ligands.

[0990] The autoclave was pressurized with ethylene to 689 kPa andcontinuously fed ethylene with stirring for 4.5 hr; the internaltemperature was very steady at 60° C. The ethylene was vented and theproduct, a clear yellow solution, was rinsed out of the autoclave withchloroform, rotary evaporated, and held under high vacuum overnight toyield 1.56 g of thin light-brown liquid ethylene/methyl acrylatecopolymer. The infrared spectrum of the product exhibited a strong estercarbonyl stretch at 1740 cm⁻¹. ¹H-1 NMR analysis (CDCl₃): 61 methylcarbons per 1000 methylene carbons. Comparison of the integrals of theester methoxy (3.67 ppm) and ester methylene (CH ₂COOMe; 2.30 ppm) peakswith the integrals of the carbon chain methyls (0.8-0.9 ppm) andmethylenes (1.2-1.3 ppm) indicated a methyl acrylate content of 16.6 mol% (37.9 wt %). This product yield and composition represent 480 ethyleneturnovers and 96 methyl acrylate turnovers. ¹³C NMR analysis; branchingper 1000 CH₂: total methyls (48.3), Methyl (20.8), Ethyl (10.5), Propyl(1), Butyl (8), _(≧)Amyl and End of Chain (18.1), methyl acrylate(94.4); ester-bearing —CH(CH₂)_(n)CO₂CH₃ branches as a % of total ester:n≧5 (35.9), n=4 (14.3), n=1,2,3 (29.5), n=0 (20.3); chemical shifts werereferenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography(tetrahydrofuran, 30° C., polymethylmethacrylate reference, resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n)=3,370; M_(w)=5,450; M_(w)/M_(n)=1.62.

[0991] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB 120C, 0.05M CrAcAc Freq ppm Intensity 53.74432.19635 CH₂Cl₂ solvent impurity 50.9115 8.84408 50.641 132.93 45.51657.55996 MEB₀ 43.8 ppm: 2 adjacent MEB₀ 39.6917 2.71676 39.2886 7.9193338.1639 13.843 37.7926 26.6353 37.1666 20.6759 36.6733 8.65855 34.625617.6899 34.4612 16.7388 34.1429 85.624 33.9095 124.997 1EB₄+ 33.67640.0271 Contributions from EB 33.2888 11.4719 Contributions from EB32.8644 14.4963 Contributions from EB 32.3498 17.5883 Contributions fromEB 32.0475 9.83096 Contributions from EB 31.8459 30.9676 Contributionsfrom EB 31.7079 12.7737 Contributions from EB 31.5912 13.8792Contributions from EB 31.0873 19.6266 Contributions from EB 30.625810.5512 30.1324 58.6101 29.6497 169.398 29.4322 48.5318 29.1934 95.494827.8619 8.70181 27.4269 32.9529 26.9283 78.0563 26.5145 27.0608 26.355414.0683 25.4588 21.9081 2EB₄ (tent) 25.3315 9.04646 2EB₄ (tent) 24.976164.2333 2EB₅+ 24.2069 10.771 BBB (beta-beta-B) 23.0451 9.50073 2B₄22.9337 6.90528 2B₄ 22.5518 30.0427 2B₅+, EOC 19.9842 1.87415 2B₃19.6288 17.125 1B₁ 19.1673 6.0427 1B₁ 16.7695 2.23642 14.3 — 1B₃ 13.788234.0749 1B₄+, EOC 11.0774 4.50599 1B₂ 10.8705 10.8817 1B₂ 189.9891.04646 EB₀ Carbonyl 175.687 3.33867 EB₀ Carbonyl 175.406 14.4124 EB₀Carbonyl 175.22 5.43832 EB₀ Carbonyl 175.061 3.53125 EB₀ Carbonyl172.859 11.2356 EB₁+ Carbonyl 172.605 102.342 EB₁+ Carbonyl 172.097.83303 EB₁+ Carbonyl 170.944 3.294 EB₁+ Carbonyl

Example 93

[0992] A 45-mg (0.048-mmol) sample of{[(2,6-i-PrPh)₂DABAn]PdMe(Et₂O)}SbF₆ ⁻ was placed in a 600-ML Parr®stirred autoclave under nitrogen. To this was added 50 mL of dry,deaerated methylene chloride, and the autoclave was pressurized to 414kPa with ethylene. Ethylene was continuously fed at 414 kPa withstirring at 23-25° C. for 3 hr; then the feed was shut off and thereaction was stirred for 12 hr more. At the end of this time, theautoclave was under 89.6 kPa (absolute). The autoclave was repressurizedto 345 kPa with ethylene and stirred for 2 hr more as the pressuredropped to 255 kPa, showing that the catalyst was still active; theethylene was then vented. The brown solution in the autoclave was rotaryevaporated, taken up in chloroform, filtered through alumina to removecatalyst, and rotary evaporated and then held under high vacuum to yield7.35 g of thick, yellow liquid polyethylene. ¹H NMR analysis (CDCl₃):131 methyl carbons per 1000 methylene carbons. Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n)=10,300; M_(w)=18,100; M_(w)/M_(n)=1.76.

Example 94

[0993] A 79-mg (0.085-mmol) sample of{[(2,6-i-PrPh)₂DABAn]PdMe(Et₂O)}SbF₆ ⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added 50 mL of dry,deaerated methyl acrylate, and the autoclave was pressurized to 689 kPawith ethylene. The autoclave was warmed to 50° C. and the reaction wasstirred at 689 kPa for 70 hr; the ethylene was then vented. The clearyellow solution in the autoclave was filtered through alumina to removecatalyst, rotary evaporated, and held under high vacuum to yield 0.27 gof liquid ethylene/methyl acrylate copolymer. The infrared spectrum ofthe product exhibited a strong ester carbonyl stretch at 1740cm⁻¹. ¹HNMR analysis (CDCl₃): 70 methyl carbons per 1000 methylene carbons; 13.5mol % (32 wt %) methyl acrylate. This yield and composition represent 12methyl acrylate turnovers and 75 ethylene turnovers.

Example 95

[0994] A 67-mg (0.089-mmol) of {[(2,4,6-MePh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻was placed in a 200-mL glass centrifuge bottle with a magnetic stir barunder nitrogen. To this was added 40 mL of dry, deaerated methylenechloride. The bottle was immediately pressurized to 207 kPa withethylene. Ethylene was continuously fed at 207 kPa with stirring at23-25° C. for 4 hr. After 4 hr, the ethylene feed was shut off and thereaction was stirred for 12 hr more. At the end of this time, the bottlewas under zero pressure (gauge). The brown solution was rotaryevaporated and held under high vacuum to yield 5.15 g of thick, brownliquid polyethylene. ¹H NMR analysis (CDCl₃): 127 methyl carbons per1000 methylene carbons. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=20,200; M_(w)=32,100;M_(w)/M_(n)=1.59.

Example 96

[0995] A 56-mg (0.066-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃)}SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave under nitrogen. To this was added 30 mL of dry,deaerated perfluoro(propyltetrahydrofuran). The autoclave was stirredand pressurized to 5.9 MPa with ethylene. The internal temperaturepeaked at 29° C.; a cool water bath was placed around the autoclavebody. The reaction was stirred for 16 hr at 23° C. and 5.9 MPa and theethylene was then vented. The autoclave contained a light yellowgranular rubber; this was scraped out of the autoclave and held underhigh vacuum to yield 29.0 g (15,700 catalyst turnovers) of spongy,non-tacky, rubbery polyethylene which had good elastic recovery and wasvery strong; it was soluble in chloroform or chlorobenzene.

[0996] The polyethylene was amorphous at room temperature: it exhibiteda glass transition temperature of −57° C. and a melting endotherm of−16° C. (35J/g) by differential scanning calorimetry. On cooling, therewas a crystallization exotherm with a maximum at 1° C. (35J/g). Uponremelting and recooling the melting endotherm and crystallizationexotherm persisted, as did the glass transition. Dynamic mechanicalanalysis at 1 Hz showed a tan δ peak at −51° C. and a peak in the lossmodulus E″ at −65° C.; dielectric analysis at 1000 Hz showed a tan dpeak at −35° C. ¹H NMR analysis (CDCl₃): 86 methyl carbons per 1000methylene carbons. ¹³C NMR analysis: branching per 1000 CH₂: totalMethyls (89.3), Methyl (37.2), Ethyl (14), Propyl (6.4), Butyl (6.9),≧Am and End Of Chain (23.8); chemical shifts were referenced to thesolvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm).Gel permeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=137,000; M_(w)=289,000; M_(w)/M_(n)=2.10.Intrinsic viscosity (trichlorobenzene, 135° C.): 2.565 dL/g. Absolutemolecular weight averages corrected for branching: M_(n)=196,000;M_(w)=425,000; M_(w)/M_(n)=2.17. Density (determined at room temperaturewith a helium gas displacement pyrometer): 0.8546+0.0007 g/cc.

Example 97

[0997] A 49-mg (0.058 mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave under nitrogen. To this was added 30 mL of dry,deaerated hexane. The autoclave was stirred and pressurized to 5.9 MPawith ethylene. The internal temperature peaked briefly at 34° C.; a coolwater bath was placed around the autoclave body. The reaction wasstirred for 16 hr at 23° C. At 14 hr, the ethylene feed was shut off;the autoclave pressure dropped to 5.8 MPa over 2 hr; the ethylene wasthen vented. The autoclave contained a light yellow, gooey rubberswollen with hexane, which was scraped out of the autoclave and heldunder high vacuum to yield 28.2 g (17,200 catalyst turnovers) of spongy,non-tacky, rubbery polyethylene which had good elastic recovery andwhich was very strong.

[0998] The polyethylene was amorphous at room temperature: it exhibiteda glass transition temperature of −61° C. and a melting endotherm of−12° C. (27J/g) by differential scanning calorimetry. Dynamic mechanicalanalysis at 1 Hz showed a tan d peak at −52° C. and a peak in the lossmodulus E″ at −70° C.; dielectric analysis at 1000 Hz showed a tan dpeak at −37° C. ¹H NMR analysis (CDCl₃): 93 methyl carbons per 1000methylene carbons. ¹³C NMR analysis: branching per 1000 CH₂: totalMethyls (95.4), Methyl (33.3), Ethyl (17.2), Propyl (5.2), Butyl (10.8),Amyl (3.7), ≧Hex and End Of Chain (27.4); chemical shifts werereferenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=149,000;M_(w)=347,000; M_(w)/M_(n)=2.33. Density (determined at room temperaturewith a helium gas displacement pycnometer): 0.8544±0.0007 g/cc.

Example 98

[0999] Approximately 10-mesh silica granules were dried at 200° C. andwere impregnated with a methylene chloride solution of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ to give a 10 wt % loadingof the catalyst on silica.

[1000] A 0.53-g (0.063 mmol) sample of silica gel containing 10 wt %{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave under nitrogen. To this was added 40 mL of dry,deaerated hexane. The autoclave was stirred and pressurized to 5.5 MPawith ethylene; the ethylene feed was then turned off. The internaltemperature peaked briefly at 31° C. The reaction was stirred for 14 hrat 23° C. as the pressure dropped to 5.3 MPa; the ethylene was thenvented. The autoclave contained a clear, yellow, gooey rubber swollenwith hexane. The product was dissolved in 200 mL chloroform, filteredthrough glass wool, rotary evaporated, and held under high vacuum toyield 7.95 g (4500 catalyst turnovers) of gummy, rubbery polyethylene.¹H NMR analysis (CDCl₃): 96 methyl carbons per 1000 methylene carbons.Gel permeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=6,900; M_(w)=118,000; M_(w)/M_(n)=17.08.

Example 99

[1001] A 108-mg (0.073 mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}BAF⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added via syringe 75 mL ofdeaerated reagent grade methyl acrylate containing 100 ppm hydroquinonemonomethyl ether and 100 ppm of phenothiazine. The autoclave waspressurized to 5.5 MPa with ethylene and was stirred at 35° C. asethylene was continuously fed for 90 hr; the ethylene was then vented.The product consisted of a swollen clear foam wrapped around theimpeller; 40 mL of unreacted methyl acrylate was poured off the polymer.The polymer was stripped off the impeller and was held under high vacuumto yield 38.2 g of clear, grayish, somewhat-tacky rubber. ¹H NMRanalysis (CDCl₃): 99 methyl carbons per 1000 methylene carbons.Comparison of the integrals of the ester methoxy (3.67 ppm) and estermethylene (CH ₂COOMe; 2.30 ppm) peaks with the integrals of the carbonchain methyls (0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated amethyl acrylate content of 0.9 mol % (2.6 wt %). This product yield andcomposition represent 18,400 ethylene turnovers and 158 methyl acrylateturnovers. ¹³C NMR analysis: branching per 1000 CH₂: total Methyls(105.7), Methyl (36.3), Ethyl (22), Propyl (4.9), Butyl (10.6), Amyl(4), ≧Hex and End Of Chain (27.8), methyl acrylate (3.4); ester-bearing—CH(CH₂)_(n)CO₂CH₃ branches as a % of total ester: n≧5 (40.6), n=1,2,3(2.7), n=0 (56.7); chemical shifts were referenced to the solvent: thehigh field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeationchromatography (tetrahydrofuran, 30° C., polymethylmethacrylatereference, results calculated as polymethylmethacrylate using universalcalibration theory): M_(n)=151,000; M_(w)=272,000; M_(w)/M_(n)=1.81.

Example 100

[1002] A 62-mg. (0.074-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen with 200 mL of deaerated aqueous 10%(v/v) n-butanol. The autoclave was pressurized to 2.8 MPa with ethyleneand was stirred for 16 hr. The ethylene was vented and the polymersuspension was filtered. The product consisted of a fine gray powderypolymer along with some larger particles of sticky black polymer; thepolymer was washed with acetone and dried to yield 0.60 g (290 catalystturnovers) of polyethylene. The gray polyethylene powder was insolublein chloroform at RT; it was soluble in hot tetrachloroethane, but formeda gel on cooling to RT. ¹H NMR analysis (tetrachloroethane-d₂; 100° C.):43 methyl carbons per 1000 methylene carbons. Differential scanningcalorimetry exhibited a melting point at 89° C. (78J/g) with a shoulderat 70° C.; there was no apparent glass transition.

Example 101

[1003] A 78-mg (0.053-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}BAF⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added 40 mL of dry,deaerated t-butyl acrylate containing 100 ppm hydroquinone monomethylether. The autoclave was pressurized with ethylene to 2.8 MPa and wasstirred and heated at 35° C. as ethylene was continuously fed at 2.8 MPafor 24 hr; the ethylene was then vented. The product consisted of ayellow, gooey polymer which was dried under high vacuum to yield 6.1 gof clear, yellow, rubbery ethylene/t-butyl acrylate copolymer which wasquite tacky. ¹H NMR analysis (CDCl₃): 102 methyl carbons per 1000methylene carbons. Comparison of the integral of the ester t-butoxy(1.44 ppm) peak with the integrals of the carbon chain methyls (0.8-0.9ppm) and methylenes (1.2-1.3 ppm) indicated a t-butyl acrylate contentof 0.7 mol % (3.3 wt %). This yield and composition represent 3960ethylene turnovers and 30 t-butyl acrylate turnovers. Gel permeationchromatography (tetrahydrofuran, 30° C., polymethylmethacrylatereference, results calculated as polymethylmethacrylate using universalcalibration theory): M_(n)=112,000; M_(w)=179,000; M_(w)/M_(n)=1.60.

Example 102

[1004] A 19-mg (0.022-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave under nitrogen. The autoclave was pressurized to5.2 MPa with ethylene and was stirred for 2 hr; the ethylene feed wasthen shut off. The autoclave was stirred for 16 hr more as the ethylenepressure dropped to 5.0 MPa; the ethylene was then vented. The autoclavecontained a light yellow, granular sponge rubber growing all over thewalls and head of the autoclave; this was scraped out to yield 13.4 g(21,800 catalyst turnovers) of spongy, non-tacky, rubbery polyethylenewhich was very strong and elastic. ¹H NMR analysis (CDCl₃): 90 methylcarbons per 1000 methylene carbons.

[1005] Differential scanning calorimetry exhibited a glass transition at−50° C. Gel permeation chromatography (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=175,000; M_(w)=476,000;M_(w)/M_(n)=2.72.

Example 103

[1006] A 70-mg (0.047-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}BAF⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added 70 mL of deaeratedreagent grade methyl acrylate containing 100 ppm each hydroquinonemonomethyl ether and phenothiazine and 0.7 mL (1 wt %; 4.7 mol %)deaerated, deionized water. The autoclave was stirred at 35° C. asethylene was continuously fed at 4.8 MPa for 16 hr; the ethylene wasthen vented. The product consisted of a clear solution. Rotaryevaporation yielded 1.46 g of ethylene/methyl acrylate copolymer as aclear oil. The infrared spectrum of the product exhibited a strong estercarbonyl stretch at 1740cm⁻¹. ¹H NMR analysis (CDCl₃): 118 methylcarbons per 1000 methylene carbons. Comparison of the integrals of theester methoxy (3.67 ppm) and ester methylene (CH ₂COOMe; 2.30 ppm) peakswith the integrals of the carbon chain methyls (0.8-0.9 ppm) andmethylenes (1.2-1.3 ppm) indicated a methyl acrylate content of 0.7 mol% (2.2 wt %). This product yield and composition represent 1090 ethyleneturnovers and 8 methyl acrylate turnovers. Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=362; M_(w)=908;M_(w)/M_(n)=2.51.

Example 104

[1007] A 53-mg (0.036-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}BAF⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added 100 mL of dry,deaerated methylene chloride. The autoclave was immersed in a cool waterbath and stirred as it was pressurized to 4.8 MPa with ethylene.Ethylene was continuously fed with stirring at 4.8 MPa and 23° C. for 23hr; the ethylene then was vented. The product consisted of a clearrubber, slightly swollen described in a somewhat different way above,and they may be described as “polyolefins” even though they may containother monomer units which are not olefins (e.g., olefinic esters). Inthe polymerization of an unsaturated compound of the formulaH₂C═CH(CH₂)_(e)G, wherein e is 0 or an integer of 1 or more, and G ishydrogen or —CO₂R¹, the usual (“normal”) polymeric repeat unit obtainedwould be —CH₂—CH[(CH₂)_(e)G]—, wherein the branch has the formula—(CH₂)_(e)G. However, with some of the instant catalysts a polymericunit may be —CH₂—CH[(CH₂)_(f)G]—, wherein f≠e, and f is 0 or an integerof 1 or more. If f<e, the “extra” methylene groups may be part of themain polymer chain. If f>e (parts of) additional monomer molecules maybe incorporated into that branch. In other words, the structure of anypolymeric unit may be irregular and different for monomer moleculesincorporated into the polymer, and the structure of such a polymericunit obtained could be rationalized as the result of “migration of theactive polymerizing site” up and down the polymer chain, although thismay not be the actual mechanism. This is highly unusual, particularlyfor polymerizations employing transition metal coordination catalysts.

[1008] For “normal” polymerizations, wherein the polymeric unit—CH₂—CH[(CH₂)_(e)G]— is obtained, the theoretical amount of branching,as measured by the number of branches per 1000 methylene (—CH₂—) groupscan be calculated as follows which defines terms “theoretical branches”or “theoretical branching” herein:${{Theoretical}\quad {branches}} = \frac{{1000 \circ {Total}}\quad {mole}\quad {fraction}\quad {of}\quad \alpha \text{-}{olefins}}{\begin{matrix}\{ {\lbrack {\Sigma ( {{{2 \circ {mole}}\quad {fraction}\quad e} = 0} )} \rbrack +}  \\ \lbrack {\Sigma( {{mole}\quad {fraction}\quad \alpha \text{-}{{olefin} \circ e}} )} \rbrack \}\end{matrix}}$

[1009] In this equation, an α-olefin is any olefinic compoundH₂C═CH(CH₂)_(e)G wherein e≠0. Ethylene or an acrylic compound are thecases wherein e=0. Thus to calculate with methylene chloride. Thepolymer was dried under high vacuum at room temperature to yield 34.5 g(34,100 catalyst turnovers) of clear rubbery polyethylene. ¹H NMRanalysis (CDCl₃): 110 methyl carbons per 1000 methylene carbons. Gelpermeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=243,000; M_(w)=676,000; M_(w)/M_(n)=2.78.

Example 104

[1010] A 83-mg (0.056-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}BAF⁻ was placed in a 600-mL Parr®stirred autoclave under nitrogen. To this was added 70 mL of dry,deaerated, ethanol-free chloroform. The autoclave was immersed in a coolwater bath and stirred as it was pressurized to 4.7 MPa with ethylene.Ethylene was continuously fed with stirring at 4.7 MPa and 23° C. for 21hr; the ethylene then was vented. The product consisted of a pink,rubbery, foamed polyethylene, slightly swollen with chloroform. Thepolymer was dried under vacuum at 40° C. to yield 70.2 g (44,400catalyst turnovers) of pink, rubbery polyethylene which was slightlytacky. ¹H NMR analysis (CDCl₃): 111 methyl carbons per 1000 methylenecarbons. Gel permeation chromatography (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=213,000; M_(w)=728,000;M_(w)/M_(n)=3.41.

Example 105

[1011] A 44-mg (0.052-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was magnetically stirredunder nitrogen in a 50-mL Schlenk flask with 20 mL of dry, deaeratedmethylene chloride. To this was added 5 mL (5.25 g; 73 mmol) of freshlydistilled acrylic acid (contains a few ppm of phenothiazine as a radicalpolymerization inhibitor) via syringe and the mixture was immediatelypressurized with ethylene at 5.52 kPa and stirred for 40 hr. The darkyellow solution was rotary evaporated and the residue was stirred with50 mL water for 15 min to extract any acrylic acid homopolymer. Thewater was drawn off with a pipette and rotary evaporated to yield 50 mgof dark residue. The polymer which had been water-extracted was heatedunder high vacuum to yield 1.30 g of ethylene/acrylic acid copolymer asa dark brown oil. The infrared spectrum showed strong COOH absorbancesat 3400-2500 and at 1705 cm⁻¹, as well as strong methylene absorbancesat 3000-2900 and 1470 cm⁻¹.

[1012] A 0.2-g sample of the ethylene/acrylic acid copolymer was treatedwith diazomethane in ether to esterify the COOH groups and produce anethylene/methyl acrylate copolymer. The infrared spectrum of theesterified copolymer showed a strong ester carbonyl absorbance at 1750cm⁻¹; the COOH absorbances were gone. ¹H NMR analysis (CDCl₃): 87 methylcarbons per 1000 methylene carbons. Comparison of the integrals of theester methoxy (3.67 ppm) and ester methylene (CH ₂COOMe; 2.30 ppm) peakswith the integrals of the carbon chain methyls (0.8-0.9 ppm) andmethylenes (1.2-1.3 ppm) indicated a methyl acrylate content of 5.3 mol% (14.7 wt % methyl acrylate=>12.3 wt % acrylic acid in the originalcopolymer). This product yield and composition represent 780 ethyleneturnovers and 43 acrylic acid turnovers. Gel permeation chromatography(tetrahydrofuran, 30° C., polymethylmethacrylate reference, resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n)=25,000; M_(w)=42,800; M_(w)/M_(n)=1.71.

[1013] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data CDCl₃, 0.05M CrAcAc, 3OC Freq ppm Intensity51.0145 24.9141 45.434 1.11477 MEB₀ 38.8925 2.29147 38.5156 6.5127137.3899 10.7484 37.0713 17.3903 36.7634 17.6341 36.4182 3.57537 36.29616.0822 34.459 2.158 34.0289 9.49713 33.7369 34.4456 33.3705 49.264632.8926 18.2918 32.3935 10.5014 32.0271 3.5697 3B₅ 31.5705 30.6837 3B₆+,3EOC 31.1723 1.54526 29.813 46.4503 29.3511 117.987 29.1387 21.03428.9953 30.603 28.613 7.18386 27.2007 8.02265 26.744 23.8731 26.377746.8498 26.006 5.42389 25.5547 8.13592 25.0609 5.46013 2 EB₄(tentative)24.9175 2.30355 2 EB₄(tentative) 24.6042 15.7434 2 EB₅+ 23.7547 2.7891423.3777 5.63727 22.7936 8.07071 2B₄ 22.6768 3.78032 2B₄ 22.3211 33.16032B₅+, 2EOC 19.3477 15.4369 1B₁ 18.8645 5.97477 1B₁ 14.1814 1.99297 1B₃13.7407 38.5361 1B₄+, 1EOC 11.0274 6.19758 1B₂ 10.5124 10.4707 1B₂176.567 9.61122 EB₀ carbonyl 174.05 9.03673 EB₁+ carbonyl 173.779 85.021EB₁+ carbonyl

Example 106

[1014] A 25-mg (0.029-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was magnetically stirredunder 55.2 kPa of ethylene in a 50-mL Schlenk flask with 20 mL of drymethylene chloride and 5 mL (4.5 g; 39 mmol) of methyl 4-pentenoate for40 hr at room temperature. The yellow solution was rotary evaporated toyield 3.41 g of ethylene/methyl 4-pentenoate copolymer as a yellow oil.The infrared spectrum of the copolymer showed a strong ester carbonylabsorbance at 1750 cm⁻¹. ¹H NMR analysis (CDCl₃): 84 methyl carbons per1000 methylene carbons. Comparison of the integrals of the ester methoxy(3.67 ppm) and ester methylene (CH ₂COOMe; 2.30 ppm) peaks with theintegrals of the carbon chain methyls (0.8-0.9 ppm) and methylenes(1.2-1.3 ppm) indicated a methyl 4-pentenoate content of 6 mol % (20 wt%). This yield and composition represent about 3400 ethylene turnoversand 200 methyl 4-pentenoate turnovers. ¹³C NMR quantitative analysis:branching per 1000 CH₂: total Methyls (93.3), Methyl (37.7),Ethyl(18.7), Propyl (2), Butyl (8.6), ≧Am and end of chains (26.6), ≧Buand end of chains (34.8); ester-bearing branches —CH(CH₂)_(n)CO₂CH₃ as a% of total ester: n≧5 (38.9), n=4 (8.3), n=1,2,3 (46.8), n=0 (6);chemical shifts were referenced to the solvent: chloroform-d₁ (77 ppm).Gel permeation chromatography (tetrahydrofuran, 300° C.,polymethylmethacrylate reference, results calculated aspolymethylmethacrylate using universal calibration theory):M_(n)=32,400; M_(w)=52,500; M_(w)/M_(n)=1.62.

Example 107

[1015] A 21-mg (0.025-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was magnetically stirredunder nitrogen in a 50-mL Schlenk flask with 5 mL of dry methylenechloride and 5 mL (4.5 g; 39 mmol) of methyl 4-pentenoate for 74 hr. Theyellow solution was rotary evaporated to yield 0.09 g of a yellow oil,poly[methyl 4-pentenoate]. The infrared spectrum showed a strong estercarbonyl absorbance at 1750 cm⁻¹. The ¹H NMR (CDCl₃) spectrum showedolefinic protons at 5.4-5.5 ppm; comparing the olefin integral with theintegral of the ester methoxy at 3.67 ppm indicates an average degree ofpolymerization of 4 to 5. This example demonstrates the ability of thiscatalyst to homopolymerize alpha olefins bearing polar functional groupsnot conjugated to the carbon-carbon double bond.

Example 108

[1016] A 53-mg (0.063-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂C(O)CH₃}SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave under nitrogen. To this was added 25 mL of dry,deaerated toluene and 25 mL (26 g; 0.36 mol) of freshly distilledacrylic acid containing about 100 ppm phenothiazine. The autoclave waspressurized to 2.1 MPa with ethylene and was stirred for 68 hr at 23°C.; the ethylene was then vented. The autoclave contained a colorless,hazy solution. The solution was rotary evaporated and the concentratewas taken up in 50 mL of chloroform, filtered through diatomaceousearth, rotary evaporated, and then held under high vacuum to yield 2.23g of light brown, very viscous liquid ethylene/acrylic acid copolymer.The infrared spectrum showed strong COOH absorbances at 3400-2500 and at1705 cm⁻¹, as well as strong methylene absorbances at 3000-2900 and 1470cm⁻¹.

[1017] A 0.3-g sample of the ethylene/acrylic acid copolymer was treatedwith diazomethane in ether to esterify the COOH groups and produce anethylene/methyl acrylate copolymer. The infrared spectrum showed astrong ester carbonyl absorbance at 1750 cm⁻¹; the COOH absorbances weregone. ¹H NMR analysis (CDCl₃): 96 methyl carbons per 1000 methylenecarbons. Comparison of the integrals of the ester methoxy (3.67 ppm) andester methylene (CH ₂COOMe; 2.30 ppm) peaks with the integrals of thecarbon chain methyls (0.8-0.9 ppm) and methylenes (1.2-1.3 ppm)indicated a methyl acrylate content of 1.8 mol % (5.4 wt % methylacrylate=>4.5 wt % acrylic acid in the original copolymer). This productyield and composition represent 1200 ethylene turnovers and 22 acrylicacid turnovers. Gel permeation chromatography (trichlorobenzene, 135°C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=5,330; M_(w)=15,000;M_(w)/M_(n)=2.82.

Example 109

[1018] A 600-mL stirred Parr® autoclave was sealed and flushed withnitrogen. Fifty mL (48 g; 0.56 mol) of dry, deaerated methyl acrylatewas introduced into the autoclave via gas tight syringe through a porton the autoclave head. Then 60 mg (0.07 mmol) of{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}BAF⁻ was introduced into the autoclavein the following manner: a 2.5-mL gas tight syringe with a syringe valvewas loaded with 60 mg of {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}BAF⁻ undernitrogen in a glove box; then 1 mL of dry, deaerated methylene chloridewas drawn up into the syringe and the contents were quickly injectedinto the autoclave through a head port. This method avoids having thecatalyst in solution with no stabilizing ligands.

[1019] The autoclave body was immersed in a running tap water bath; theinternal temperature was very steady at 22° C. The autoclave waspressurized with ethylene to 2.8 MPa and continuously fed ethylene withstirring for 4.5 hr. The ethylene was then vented and the product, amixture of methyl acrylate and yellow gooey polymer, was rinsed out ofthe autoclave with chloroform, rotary evaporated, and held under highvacuum overnight to yield 4.2 g of thick, light-brown liquidethylene/methyl acrylate copolymer. The infrared spectrum of the productexhibited a strong ester carbonyl stretch at 1740 cm⁻¹. ¹H NMR analysis(CDCl₃): 82 methyl carbons per 1000 methylene carbons. Comparison of theintegrals of the ester methoxy (3.67 ppm) and ester methylene (CH₂COOMe; 2.30 ppm) peaks with the integrals of the carbon chain methyls(0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated a methyl acrylatecontent of 1.5 mol % (4.4 wt %). This product yield and compositionrepresent 2000 ethylene turnovers and 31 methyl acrylate turnovers. ¹³CNMR analysis: branching per 1000 CH₂: total Methyls (84.6), Methyl(28.7), Ethyl (15.5), Propyl (3.3), Butyl (8.2), ≧Hex and End Of Chain(23.9), methyl acrylate (13.9). Ester-bearing —CH(CH2)_(n)CO2CH3branches as a % of total ester: n≧5 (34.4), n=4 (6.2), n=1,2,3 (13), n=0(46.4). Mole %: ethylene (97.6), methyl acrylate (2.4); chemical shiftswere referenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography(tetrahydrofuran, 30° C., polymethylmethacrylate reference, resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n)=22,000; M_(w)=45,500; M_(w)/M_(n)=2.07.

[1020] A mixture of 1.45 g of this ethylene/methyl acrylate copolymer,20 mL dioxane, 2 mL water, and 1 mL of 50% aqueous NaOH was magneticallystirred at reflux under nitrogen for 4.5 hr. The liquid was thendecanted away from the swollen polymer and the polymer was stirredseveral hours with three changes of boiling water. The polymer wasfiltered, washed with water and methanol, and dried under vacuum (80°C./nitrogen purge) to yield 1.2 g soft of ionomer rubber, insoluble inhot chloroform. The FTIR-ATR spectrum of a pressed film (pressed at 125°C./6.9 MPa) showed a strong ionomer peak at 1570 cm⁻¹ and virtually noester carbonyl at 1750 cm⁻¹. The pressed film was a soft, slightly tackyrubber with about a 50% elongation to break. This example demonstratesthe preparation of an ionomer from this ethylene/methyl acrylatepolymer.

Example 110

[1021] The complex [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.020 g, 0.036 mmol) wasweighed into a vial and dissolved in 6 ml CH₂Cl₂. NaBAF (0.032 g, 0.036mmol) was rinsed into the stirring mixture with 4 ml of CH₂Cl₂. Therewas an immediate color change from orange to yellow. The solution wasstirred under 6.2 MPa ethylene in a Fisher Porter tube with temperaturecontrol at 19° C. The internal temperature rose to 22° C. during thefirst 15 minutes. The temperature controller was raised to 30° C. After35 minutes, the reaction was consuming ethylene slowly. After a totalreaction time of about 20 h, there was no longer detectable ethyleneconsumption, but the liquid level in the tube was noticeably higher.Workup by addition to excess MeOH gave a viscous liquid precipitate. Theprecipitate was redissolved in CH₂Cl₂, filtered through a 0.5 micronPTFE filter and reprecipitated by addition to excess MeOH to give 7.208g dark brown viscous oil (7180 equivalents of ethylene per Pd). ¹H NMR(CDCl₃) 0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂). Integration allowscalculation of branching: 118 methyl carbons per 1000 methylene carbons.GPC in THF vs. PMMA standard: M_(n)=12,700, M_(w)=28,800,M_(w)/M_(n)=2.26.

Example 111

[1022] The solid complex {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ (0.080g, 0.096 mmol) was placed in a Schlenk flask which was evacuated andrefilled with ethylene twice. Under one atm of ethylene, black spotsformed in the center of the solid complex and grew outward as ethylenewas polymerized in the solid state and the resulting exotherm destroyedthe complex. Solid continued to form on the solid catalyst that had notbeen destroyed by the exotherm, and the next day the flask containedconsiderable solid and the reaction was still slowly consuming ethylene.The ethylene was disconnected and 1.808 g of light gray elastic solidwas removed from the flask (644 equivalents ethylene per Pd). The ¹H NMRin CDCl₃ was similar to example 110 with 101 methyl carbons per 1000methylene carbons. Differential Scanning Calorimetry (DSC): first heat25 to 150° C., 15° C./min, no events; second heat −150 to 150° C.,T_(g)=−53° C. with an endothermic peak centered at −20° C.; third heat−150 to 275° C., T_(g)=−51° C. with an endothermic peak centered at −20°C. GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):M_(n)=13,000 M_(w)=313,000 M_(w)/M_(n)=24.

Example 112

[1023] The complex {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ (0.084 g,0.100 mmol) was loaded into a Schlenk flask in the drybox followed by 40ml of dry dioxane. The septum-capped flask was connected to a Schlenkline and the flask was then briefly evacuated and refilled withethylene. The light orange mixture was stirred under an ethyleneatmosphere at slightly above 1 atm by using a mercury bubbler. There wasrapid uptake of ethylene. A room temperature water bath was used tocontrol the temperature of the reaction. After 20 h, the reaction wasworked up by removing the solvent in vacuo to give 10.9 g of a highlyviscous fluid (3870 equivalents of ethylene per Pd). Dioxane is asolvent for the Pd complex and a non-solvent for the polymer product. ¹HNMR (CDCl₃) 0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂). Integrationallows calculation of branching: 100 methyl carbons per 1000 methylenecarbons. GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):Partially resolved trimodal distribution with M_(n)=16300, M_(w)=151000M_(w)/M_(n)=9.25. DSC (second heat, −150° C. to 150° C., 15° C./min)T_(g)=−63° C., endothermic peak centered at −30° C.

Example 113

[1024] Polymerization of ethylene was carried out according to example112, using pentane as solvent. Pentane is a non-solvent for the Pdcomplex and a solvent for the polymer product. The reaction gave 7.47 gof dark highly viscous fluid (2664 equivalents of ethylene per Pd). ¹HNMR analysis (CDCl₃): 126 methyl carbons per 1000 methylene carbons. ¹³CNMR analysis, branching per 1000 CH₂: Total methyls (128.8), Methyl(37.8), Ethyl (27.2), Propyl (3.5), Butyl (14.5), Amyl (2.5), ≧Hexyl andend of chain (44.7), average number of carbon atoms for ≧Hexylbranches=16.6 (calculated from intrinsic viscosity and GPC molecularweight data). Quantitation of the —CH₂CH(CH₃)CH₂CH₃ structure per 1000CH₂'s: 8.3. These side chains are counted as a Methyl branch and anEthyl branch in the quantitative branching analysis. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=9,800,M_(w)=16,100, M_(w)/M_(n)=1.64. Intrinsic viscosity (trichlorobenzene,135° C.)=0.125 g/dL. Absolute molecular weights calculated by GPC(trichlorobenzene, 135° C., polystyrene reference, corrected forbranching using measured intrinsic viscosity): M_(n)=34,900,M_(w)=58,800, M_(w)/M_(n)=1.68. DSC (second heat, −150° C. to 150° C.,15° C./min) T_(g)=−71° C., endothermic peak centered at −43° C.

Example 114

[1025] Polymerization of ethylene was carried out according to example112, using distilled degassed water as the medium. Water is anon-solvent for both the Pd complex and the polymer product. The mixturewas worked up by decanting the water from the product which was thendried in vacuo to give 0.427 g of dark sticky solid (152 equivalents ofethylene per Pd). ¹H NMR analysis (CDCl₃): 97 methyl carbons per 1000methylene carbons. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as linear polyethylene using universalcalibration theory): M_(n)=25,100, M_(w)=208,000, M_(w)/M_(n)=8.31.

Example 115

[1026] Polymerization of ethylene was carried out according to example112, using 2-ethylhexanol as the solvent. The Pd complex is sparinglysoluble in this solvent and the polymer product is insoluble. Thepolymer product formed small dark particles of high viscosity liquidsuspended in the 2-ethylhexanol. The solvent was decanted and thepolymer was dissolved in CHCl₃ and reprecipitated by addition of excessMeOH. The solvent was decanted, and the reprecipitated polymer was driedin vacuo to give 1.66 g of a dark highly viscous fluid (591 equivalentsof ethylene per Pd). ¹H NMR analysis (CDCl₃): 122 methyl carbons per1000 methylene carbons. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as linear polyethylene using universalcalibration theory): M_(n)=7,890, M_(w)=21,600, M_(w)/M_(n)=2.74.

Example 116

[1027] The solid complex {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ (0.084g, 0.100 mmol) was loaded into a Schlenk flask in the drybox. The flaskwas connected to a Schlenk line under 1 atm of ethylene, and cooled to−78° C. Solvent, (CH₂Cl₂, 40 ml) was added by syringe and afterequilibrating at −78° C. under ethylene, the mixture was warmed to roomtemperature under ethylene. The mixture was stirred under an ethyleneatmosphere at slightly above 1 atm by using a mercury bubbler. There wasrapid uptake of ethylene. A room temperature water bath was used tocontrol the temperature of the reaction. After 24 h, the reaction wasworked up by removing the solvent in vacuo to give 24.5 g of a highlyviscous fluid (8730 equivalents of ethylene per Pd). CH₂Cl₂ is a goodsolvent for both the Pd complex and the polymer product. The polymer wasdissolved in CH₂Cl₂, and reprecipitated by addition to excess MeOH in atared flask. The solvent was decanted, and the reprecipitated polymerwas dried in vacuo to give 21.3 g of a dark highly viscous fluid. ¹H NMRanalysis (CDCl₃): 105 methyl carbons per 1000 methylene carbons. C-13NMR analysis, branching per 1000 CH₂: Total methyls (118.6), Methyl(36.2), Ethyl (25.9), Propyl (2.9), Butyl (11.9), Amyl (1.7), ≧Hexyl andend of chains (34.4), average number of carbon atoms for ≧Hexylbranches=22.5 (calculated from intrinsic viscosity and GPC molecularweight data). Quantitation of the —CH₂CH(CH₃)CH₂CH₃ structure per 1000CH₂'s: 8.1. These side chains also counted as a Methyl branch and anEthyl branch in the quantitative branching analysis. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=25,800,M_(w)=45,900, M_(w)/M_(n)=1.78. Intrinsic viscosity (trichlorobenzene,135° C.)=0.24 g/dL. Absolute molecular weights calculated by GPC(trichlorobenzene, 135° C., polystyrene reference, corrected forbranching using measured intrinsic viscosity): M_(n)=104,000,M_(w)=188,000, M_(w)/M_(n)=1.81.

[1028] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data TCB, 120C, 0.06M CrAcAc Freq ppm Intensity39.7233 5.12305 39.318 17.6892 MB₂ 38.2022 17.9361 MB₃+ 37.8369 32.3419MB₃+ 37.2469 43.1136 αB₁, 3B₃ 36.8335 10.1653 αB₁, 3B₃ 36.7452 14.674αB₁, 3B₃ 34.9592 10.3554 αγ + B, (4B₄, 5B₅, etc.) 34.6702 24.015 αγ + B,(4B₄, 5B₅, etc.) 34.5257 39.9342 α### + B, (4B₄, 5B₅, etc.) 34.2006109.158 α### + B, (4B₄, 5B₅, etc.) 33.723 36.1658 α### + B, (4B₄, 5B₅,etc.) 33.3136 12.0398 MB₁ 32.9323 20.7242 MB₁ 32.4266 6.47794 3B₅31.9409 96.9874 3B₆+, 3EOC 31.359 15.2429 ### + ### + B, 3B₄ 31.098119.2981 ### + γ + B, 3B₄ 30.6606 15.8689 ### + ### + B, 3B₄ 30.227196.7986 ### + ### + B, 3B₄ 30.1188 54.949 ### + ### + B, 3B₄ 29.7455307.576 ### + ### + B, 3B₄ 29.5809 36.2391 ### + ### + B, 3B₄ 29.336179.3542 ### + ### + B, 3B₄ 29.2157 23.0783 ### + ### + B, 3B₄ 27.642424.2024 β### + B, 2B₂, (4B₅, etc.) 27.526 29.8995 β### + B, 2B₂, (4B₅,etc.) 27.3534 23.1626 β### + B, 2B₂, (4B₅, etc.) 27.1607 70.8066 β### +B, 2B₂, (4B₅, etc.) 27.0042 109.892 β### + B, 2B₂, (4B₅, etc.) 26.59087.13232 β### + B, 2B₂, (4B₅, etc.) 26.3941 23.945 β### + B, 2B₂, (4B₅,etc.) 25.9446 4.45077 β### + B, 2B₂, (4B₅, etc.) 24.4034 9.52585 ββB24.2428 11.1161 ββB 23.1391 21.2608 2B₄ 23.0227 11.2909 2B₄ 22.6494103.069 2B₅+, 2EOC 20.0526 5.13224 2B₃ 19.7355 37.8832 1B₁ 19.201714.8043 1B₁, Structure XXVII 14.4175 4.50604 1B₃ 13.9118 116.163 1B₄+,1EOC 11.1986 18.5867 1B₂, Structure XXVII 10.9617 32.3855 1B₂

Example 117

[1029] Polymerization of ethylene was carried out according to example116, at a reaction temperature of 0° C. and reaction time of severalhours. The polymer product formed a separate fluid phase on the top ofthe mixture. The reaction was quenched by adding 2 ml acrylonitrile. Theproduct was moderately viscous fluid, 4.5 g (1600 equivalents ofethylene per Pd). ¹H NMR analysis (CDCl₃): 108 methyl carbons per 1000methylene carbons. ¹³C NMR analysis, branching per 1000 CH₂: Totalmethyls (115.7), Methyl (35.7), Ethyl (24.7), Propyl (2.6), Butyl(11.2), Amyl (3.2), ≧Hexyl and end of chain (37.1). Quantitation of the—CH₂CH(CH₃)CH₂CH₃ structure per 1000 CH₂'s: 7.0. These side chains arecounted as a Methyl branch and an Ethyl branch in the quantitativebranching analysis. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as linear polyethylene using universalcalibration theory: M_(n)=15,200, M_(w)=23,700, M_(w)/M_(n)=1.56.

Example 118

[1030] The Pd complex {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻(0.084 g, 0.100 mmol) was loaded into a Schlenk flask in the drybox, and40 ml of FC-75 was added. The septum-capped flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. The mixture was stirred under anethylene atmosphere at slightly above 1 atm by using a mercury bubbler.Both the Pd initiator and the polymer are insoluble in FC-75. After 15days, the reaction flask contained a large amount of gray elastic solid.The FC-75 was decanted, and the solid polymer was then dissolved inCHCl₃ and precipitated by addition of the solution to excess MeOH. Thepolymer was dried in vacuo, and then dissolved in o-dichlorobenzene at100° C. The hot solution was filtered through a 10 μm PTFE filter. Thefiltered polymer solution was shaken in a separatory funnel withconcentrated sulfuric acid, followed by distilled water, followed by 5%NaHCO₃ solution, followed by two water washes. The polymer appeared tobe a milky suspension in the organic layer during this treatment. Afterwashing, the polymer was precipitated by addition to excess MeOH in ablender and dried at room temperature in vacuo to give 19.6 g light grayelastic polymer fluff (6980 equivalents of ethylene per Pd). ¹H NMRanalysis (CDCl₃): 112 methyl carbons per 1000 methylene carbons. ¹³C NMRanalysis, branching per 1000 CH₂: Total methyls (114.2), Methyl (42.1),Ethyl (24.8), Propyl (5.1), Butyl (10.2), Amyl (4), ≧Hexyl and end ofchain (30.3), average number of carbon atoms for ≧Hexyl branches=14.4(calculated from intrinsic viscosity and GPC molecular weight data). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory: M_(n)=110,000,M_(w)=265,000, M_(w)/M_(n)=2.40. Intrinsic viscosity (trichlorobenzene,135° C.)=1.75 g/dL. Absolute molecular weights calculated by GPC(trichlorobenzene, 135° C., polystyrene reference, corrected forbranching using measured intrinsic viscosity): M_(n)=214,000,M_(w)=535,000, M_(w)/M_(n)=2.51.

Example 119

[1031] Polymerization of ethylene was carried out according to example112, using the complex {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻(0.084 g, 0.100 mmol) as the initiator and CHCl₃ as the solvent. Thereaction gave 28.4 g of dark viscous fluid (10,140 equivalents ofethylene per Pd). ¹H NMR analysis (CDCl₃): 108 methyl carbons per 1000methylene carbons. ¹³C NMR analysis, branching per 1000 CH₂: Totalmethyls (119.5), Methyl (36.9), Ethyl (25.9), Propyl (2.1), Butyl (11),Amyl (1.9), ≧Hexyl and end of chain (38.9). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as linear polyethyleneusing universal calibration theory): M_(n)=10,800, M_(w)=26,800,M_(w)/M_(n)=2.47.

Example 120

[1032] Polymerization of ethylene was carried out according to example112, using the complex [(2,6-i-PrPh)₂DABMe₂]PdMe(OSO₂CF₃) (0.068 g, 0.10mmol) as the initiator and CHCl₃ as the solvent. The reaction gave 5.98g of low viscosity fluid (2130 equivalents of ethylene per Pd). ¹H NMR(CDCl₃) 0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂); 1.5-1.7 (m, CH₃CH═CH—); 1.9-2.1 (broad, —CH ₂CH═CHCH ₂—); 5.3-5.5 (m, —CH═CH—).Integration of the olefin end groups assuming one olefin per chain givesM_(n)=630 (DP=24). A linear polymer with this molecular weight andmethyl groups at both ends should have 46 methyl carbons per 1000methylene carbons. The value measured by integration is 161, thus thispolymer is highly branched.

Example 121

[1033] Polymerization of ethylene was carried out according to example112, using the complex {[(2,6-i-PrPh)₂DABH₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻(0.082 g, 0.10 mmol) as the initiator and CHCl₃ as the solvent. Thereaction gave 4.47 g of low viscosity fluid (1600 equivalents ofethylene per Pd). ¹H NMR (CDCl₃) is similar to example 120. Integrationof the olefin end groups assuming one olefin per chain gives M_(n)=880(DP=31). A linear polymer with this molecular weight and methyl groupsat both ends should have 34 methyl carbons per 1000 methylene carbons.The value measured by integration is 156, thus this polymer is highlybranched.

Example 122

[1034] Polymerization of ethylene was carried out according to example112, using the complex{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}BCl(C₆F₅)₃ ⁻ (0.116 g, 0.10mmol) as the initiator and CHCl₃ as the solvent. The reaction gave 0.278g of low viscosity fluid, after correcting for the catalyst residue thisis 0.160 g (57 equivalents of ethylene per Pd). M_(n) estimated byintegration of olefin end groups is 300.

Example 123

[1035] The complex [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.056 g, 0.10 mmol) wasloaded into a Schlenk flask in the drybox followed by 40 ml of drytoluene. A solution of ethyl aluminum dichloride (1.37 ml of 0.08 Msolution in o-dichlorobenzene) was added while stirring. Polymerizationof ethylene was carried out using this solution according to example112. The reaction gave 0.255 g of low viscosity fluid, after correctingfor the catalyst residue this is 0.200 g (71 equivalents of ethylene perPd). M_(n) estimated by integration of olefin end groups is 1300.

Example 124

[1036] Methyl acrylate was sparged with argon, dried over activated 4Asieves, passed through activity 1 alumina B in the drybox, and inhibitedby addition of 20 ppm phenothiazine. The solid complex{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}SbF₆ ⁻ (0.084 g, 0.100 mmol) was loadedinto a Schlenk flask in the drybox. The flask was connected to a Schlenkline under 1 atm of ethylene, and cooled to −78° C. Forty ml of CH₂Cl₂was added by syringe and after equilibrating at −78° C. under ethylene,5 ml of methyl acrylate was added by syringe and the mixture was warmedto room temperature under ethylene. After 40 h, the reaction was workedup by removing the solvent in vacuo to give 3.90 g of moderately viscousfluid. Integration of the ¹H NMR spectrum showed that this copolymercontained 6.9 mole % methyl acrylate. No poly(methyl acrylate)homopolymer could be detected in this sample by ¹H NMR. ¹H NMR showsthat a significant fraction of the ester groups are located at the endsof hydrocarbon branches: 3.65(s, —CO₂CH₃, area=4.5), 2.3(t, —CH ₂CO₂CH₃,ester ended branches, area=3), 1.6(m, —CH ₂CH₂CO₂CH₃, ester endedbranches, area=3), 0.95-1.55(m, CH and other CH₂, area=73), 0.8-0.95(m,CH₃, ends of branches or ends of chains, area=9.5) This is confirmed bythe ¹³C NMR quantitative analysis: Mole %: ethylene (93.1), methylacrylate (6.9), Branching per 1000 CH₂: Total methyls (80.2), Methyl(30.1), Ethyl (16.8), Propyl (1.6), Butyl (6.8), Amyl (1.3), ≧Hexyl andend of chain (20.1), methyl acrylate (41.3), Ester branchesCH(CH₂)_(n)CO₂CH₃ as a % of total ester: n≧5 (47.8), n=4 (17.4), n=1,2,3(26.8), n=0 (8).

[1037] GPC of this sample was done in THF vs. PMMA standards using adual UV/RI detector. The outputs of the two detectors were very similar.Since the UV detector is only sensitive to the ester functionality, andthe RI detector is a relatively nonselective mass detector, the matchingof the two detector outputs shows that the ester functionality of themethyl acrylate is distributed throughout the entire molecular weightrange of the polymer, consistent with a true copolymer of methylacrylate and ethylene.

[1038] A 0.503 g sample of the copolymer was fractionated by dissolvingin benzene and precipitating partially by slow addition of MeOH. Thistype of fractionation experiment is a particularly sensitive method fordetecting a low molecular weight methyl acrylate rich component since itshould be the most soluble material under the precipitation conditions.

[1039] The precipitate 0.349 g, (69%) contained 6.9 mole % methylacrylate by ¹H NMR integration, GPC (THF, PMMA standard, RI detector):M_(n)=19,600, M_(w)=29,500, M_(w)/M_(n)=1.51. The soluble fraction 0.180g (36%) contained 8.3 mole % methyl acrylate by ¹H NMR integration, GPC(THF, PMMA standard, RI detector): M_(n)=11,700, M_(w)=19,800,M_(w)/M_(n)=1.70. The characterization of the two fractions shows thatthe acrylate content is only slightly higher at lower molecular weights.These results are also consistent with a true copolymer of the methylacrylate with ethylene.

Example 125

[1040] Methyl acrylate was sparged with argon, dried over activated 4Asieves, passed through activity 1 alumina B in the drybox, and inhibitedby addition of 20 ppm phenothiazine. The complex[(2,6-i-PrPh)₂DABMe₂]PdMe(OSO₂CF₃) (0.068 g, 0.10 mmol) was loaded intoa Schlenk flask in the drybox, and 40 ml of CHCl₃ was added followed by5 ml of methyl acrylate. The septum capped flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. The light orange mixture was stirredunder an ethylene atmosphere at slightly above 1 atm by using a mercurybubbler. After 20 h, the reaction was worked up by removing the solventand unreacted methyl acrylate in vacuo to give 1.75 g of a low viscositycopolymer.

[1041]¹³C NMR quantitative analysis: Mole %: ethylene (93), methylacrylate (7), Branching per 1000 CH₂: Total methyls (100.9), Methyl(33.8), Ethyl (19.8), Propyl (1.9), Butyl (10.1), Amyl (7.3), ≧Hexyl andend of chains (28.4), methyl acrylate (41.8). This sample is lowmolecular weight—total methyls does not include end of chain methyls.Ester branches —CH(CH₂)_(n)CO₂CH₃ as a % of total ester: n≧5 (51.3), n=4(18.4), n=1,2,3 (24), n=0 ( 6.3).

Example 126

[1042] Ethylene and methyl acrylate were copolymerized according toexample 125 with catalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}BAF⁻(0.136 g, 0.10 mmol) in CH₂Cl₂ solvent with a reaction time of 72 hoursto give 4.93 g of copolymer.

Example 127

[1043] Ethylene and methyl acrylate were copolymerized according toexample 125 with catalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆⁻ (0.084 g, 0.10 mmol) with a reaction time of 72 hours to give 8.19 gof copolymer.

Example 128

[1044] Ethylene and methyl acrylate were copolymerized according toexample 125 with catalyst {[(2,6-i-PrPh)₂DABH₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆⁻ (0.082 g, 0.10 mmol) to give 1.97 g of copolymer.

Example 129

[1045] Ethylene and methyl acrylate were copolymerized according toexample 125 with catalyst {[(2,6-i-PrPh)₂DABMe₂]PdMe(CH₃CN)}SbF₆ ⁻(0.080 g, 0.10 mmol) to give 3.42 g of copolymer. The ¹H NMR showsprimarily copolymer, but there is also a small amount of poly(methylacrylate) homopolymer.

Example 130

[1046] Ethylene and methyl acrylate (20 ml) were copolymerized in 20 mlof CHCl₃ according to example 125 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.339 g, 0.40 mmol) togive 2.17 g of copolymer after a reaction time of 72 hours. ¹³C NMRquantitative analysis: Mole %: ethylene (76.3), methyl acrylate (23.7).Branching per 1000 CH₂: Total methyls (28.7), Methyl (20.5), Ethyl(3.8), Propyl (0), Butyl (11), ≧Amyl and end of chains (13.6), methylacrylate (138.1). Ester branches —CH(CH₂)_(n)CO₂CH₃ as a % of totalester: n≧5 (38.8), n=4 (20), n=1,2,3 (15.7), n=0 (25.4).

Example 131

[1047] Ethylene and methyl acrylate (20 ml) were copolymerized in 20 mlof CHCl₃ at 50° C. for 20 hours according to example 125 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.339 g, 0.40 mmol) togive 0.795 g of copolymer. DSC (two heats, −150 to +150° C., 15° C./min)shows Tg=−48° C.

Example 132

[1048] A solution of the ligand (2,6-i-PrPh)₂DAB(Me₂) (0.045 g, 0.11mmol) dissolved in 2 ml of CHCl₃ was added to a solution of the complex[PdMe(CH₃CN)(1,5-cyclooctadiene)]⁺SbF₆ ⁻ (0.051. g, 0.10 mmol) in 2 mlof CHCl₃. This mixture was combined with 35 ml of additional CHCl₃ and 5ml of methyl acrylate in a Schlenk flask in a drybox, and then acopolymerization with ethylene was carried out according to example 125to give 1.94 g of copolymer.

Example 133

[1049] Methyl acrylate (5 ml) was added to the solid catalyst{[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}BF₄ ⁻ (0.069 g, 0.10 mmol) followed by4.0 ml of CHCl₃. The addition of methyl acrylate before the CHCl₃ isoften important to avoid deactivation of the catalyst. Acopolymerization with ethylene was carried out according to example 125to give 2.87 g of copolymer.

Characterization of poly(ethylene-co-methyl acrylate) by ¹H NMR

[1050] NMR spectra in CDCl₃ were integrated and the polymer compositionsand branching ratios were calculated. See example 124 for chemicalshifts and assignments. methyl acrylate CH₃ per CO₂CH₃ per Example Yield(g) (mole %) 1000 CH₂ 1000 CH₂ 124 3.9 6.9 80 42 125 1.75 7.1 104 45 1264.93 5.6 87 34 127 8.19 6.1 87 37 128 1.97 7.3 159 50 129 3.42 9.5 86 59130 2.17 22.8 29 137 131 0.795 41 14 262 132 1.94 6.1 80 36 133 2.87 8.270 49

Molecular Weight Characterization

[1051] GPC was done in THF using PMMA standards and an RI detectorexcept for example 133 which was done in trichlorobenzene at 135° C. vs.polystyrene reference with results calculated as linear polyethyleneusing universal calibration theory. When polymer end groups could bedetected by ¹H NMR (5.4 ppm, multiplet, —CH═CH—, internal double bond),M_(n) was calculated assuming two olefinic protons per chain. ExampleM_(n) M_(w) M_(w)/M_(n) M_(n) (¹H NMR) 124 15,500 26,400 1.70 125 1,5402,190 1.42 850 126 32,500 49,900 1.54 127 12,300 22,500 1.83 128 555 5951.07 360 129 16,100 24,900 1.55 130 800 3,180 3.98 1,800 131 1,100 13215,200 26,000 1.71 133 5,010 8,740 1.75

Example 134

[1052] Ethylene and t-butyl acrylate (20 ml) were copolymerizedaccording to example 130 to give 2.039 g of viscous fluid. ¹H NMR of thecrude product showed the desired copolymer along with residual unreactedt-butyl acrylate. The weight of polymer corrected for monomer was 1.84g. The sample was reprecipitated to remove residual monomer by slowaddition of excess MeOH to a CHCl₃ solution. The reprecipitated polymerwas dried in vacuo. ¹H NMR (CDCl₃): 2.2(t, —CH ₂CO₂C(CH₃)₃, ester endedbranches), 1.6(m, —CH ₂CH₂CO₂C(CH₃)₃, ester ended branches), 1.45(s,—C(CH₃)₃), 0.95-1.45(m, CH and other CH₂), 0.75-0.95(m, CH₃, ends ofhydrocarbon branches or ends of chains). This spectrum shows that theesters are primarily located at the ends of hydrocarbon branches;integration gave 6.7 mole % t-butyl acrylate. ¹³C NMR quantitativeanalysis, branching per 1000 CH₂: Total methyls (74.8), Methyl (27.7),Ethyl (15.3), Propyl (1.5), Butyl (8.6), ≧Amyl and end of chains (30.8),—CO₂C(CH₃)₃ ester (43.2). Ester branches —CH(CH₂)_(n)CO₂C(CH₃)₃ as a %of total ester: n≧5 (44.3), n=1,2,3,4 (37.2), n=0 (18.5). GPC (THF, PMMAstandard): M_(n)=6000 M_(w)=8310 M_(w)/M_(n)=1.39.

Example 135

[1053] Glycidyl acrylate was vacuum distilled and inhibited with 50 ppmphenothiazine. Ethylene and glycidyl acrylate (5 ml) were copolymerizedaccording to Example 125 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.084 g, 0.10 mmol).The reaction mixture was filtered through a fritted glass filter toremove chloroform insolubles, and the chloroform was removed in vacuo togive 14.1 g viscous yellow oil which still contained residual unreactedglycidyl acrylate. The sample was reprecipitated to remove residualmonomer by slow addition of excess acetone to a CHCl₃ solution. Thereprecipitated polymer was dried in vacuo to give 9.92 g of copolymercontaining 1.8 mole % glycidyl acrylate. ¹H NMR (CDCl₃): 4.4, 3.9, 3.2,2.85,

[1054] and other CH₂), 0.75-0.95(m, CH₃, ends of hydrocarbon branches orends of chains). This spectrum shows that the epoxide ring is intact,and that the glycidyl ester groups are primarily located at the ends ofhydrocarbon branches. GPC (THF, PMMA standard): M_(n)=63,100M_(w)=179,000 M_(w)/M_(n)=2.85.

[1055]¹³C NMR quantitative analysis, branching per 1000 CH₂: Totalmethyls (101.7), Methyl (32.5), Ethyl (21.3), Propyl (2.4), Butyl (9.5),Amyl (1.4), ≧Hexyl and end of chains (29.3), Ester branches—CH(CH₂)_(n)CO₂R as a % of total ester: n≧5 (39.7), n=4 (small amount),n=1,2,3 (50.7), n=0 (9.6).

[1056] A 3.24-g sample of the copolymer was dissolved in 50 mL ofrefluxing methylene chloride. A solution of 0.18 g oxalic acid dihydratein 5 mL of 1:1 chloroformacetone was added to the solution of copolymerand the solvent was evaporated off on a hot plate. The thick liquid wasallowed to stand in an aluminum pan at room temperature overnight; thepan was then placed in an oven at 70° C. for 1.5 hr followed by 110°C./vacuum for 5 hr. The cured polymer was a dark, non-tacky soft rubberwhich tore easily (it had a very short elongation to break despite itsrubberiness).

Example 136

[1057] 1-Pentene (20 ml) and methyl acrylate (5 ml) were copolymerizedin 20 ml chloroform for 96 hours using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.084 g, 0.10 mmol).The solvent and unreacted monomers were removed in vacuo to give 0.303 gcopolymer (0.219 g after correcting for catalyst residue). The ¹H NMRspectrum was similar to the ethylene/methyl acrylate copolymer ofexample 124 suggesting that many of the ester groups are located at theends of hydrocarbon branches. Integration shows that the productcontains 21 mole % methyl acrylate. There are 65 acrylates and 96methyls per 1000 methylene carbons. GPC (THF, PMMA standard): M_(n)=6400M_(w)=11200 M_(w)/M_(n)=1.76.

Example 137

[1058] Benzyl acrylate was passed through activity 1 alumina B,inhibited with 50 ppm phenothiazine, and stored over activated 4Amolecular sieves. Ethylene and benzyl acrylate (5 ml) were copolymerizedaccording to example 135 to give 11.32 g of viscous fluid. ¹H NMR of thecrude product showed a mixture of copolymer and unreacted benzylacrylate (35 wt %) The residual benzyl acrylate was removed by tworeprecitations, the first by addition of excess MeOH to a chloroformsolution, and the second by addition of excess acetone to a chloroformsolution. ¹H NMR (CDCl₃): 7.35 (broad s, —CH₂C₆ H ₅), 5.1(s, —CH ₂C₆H₅),2.35(t, —CH ₂CO₂CH₂C₆H₅, ester ended branches), 1.6(m, —CH₂CH₂CO₂CH₂C₆H₅, ester ended branches), 0.95-1.5(m, CH and other CH₂),0.75-0.95(m, CH₃, ends of hydrocarbon branches or ends of chains).Integration shows that the product contains 3.7 mole % benzyl acrylate.There are 21 acrylates and 93 methyls per 1000 methylene carbons. GPC(THF, PMMA standard): M_(n)=46,200 M_(w)=73,600 M_(w)/M_(n)=1.59.

[1059]¹³C NMR quantitative analysis, Branching per 1000 CH₂: Totalmethyls (97.2), Methyl (32.9), Ethyl (20.3), Propyl (2.4), Butyl (9.7),Amyl (2.9), ≧Hexyl and end of chains (35.2), benzyl acrylate (17.9),Ester branches —CH(CH₂)_(n)CO₂R as a % of total ester: n≧5 (44.5), n=4(7.2), n=1,2,3 (42.3), n=0 (6)

Example 138

[1060] 1-Pentene (10 ml) and ethylene (1 atm) were copolymerized in 30ml chloroform according to example 125 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.084 g, 0.10 mmol) togive 9.11 g highly viscous yellow oil The ¹H NMR spectrum was similar tothe poly(ethylene) of example 110 with 113 methyl carbons per 1000methylene carbons. ¹³C NMR quantitative analysis, branching per 1000CH₂: Total methyls (119.5), Methyl (54.7), Ethyl (16.9), Propyl (8.4),Butyl (7.7), Amyl (7.2), ≧Hexyl and end of chains (30.9). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=25,000,M_(w)=44,900, M_(w)/M_(n)=1.79.

[1061] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data TCB, 120 C., 0.05 M CrAcAc Freq ppm Intensity39.6012 5.53532 39.4313 6.33425 MB₂ 38.3004 8.71403 MB₃+ 37.9446 17.7325MB₃+ 37.2809 36.416 αB₁, 3B₃ 36.7659 5.10586 αB₁, 3B₃ 34.3181 56.1758αγ + B 33.8243 15.6271 αγ + B 33.3942 8.09189 MB₁ 32.9854 20.3523 MB₁32.6721 4.35239 MB₁ 32.327 4.06305 3B₅ 31.9394 27.137 3B₆+, 3 EOC31.4031 9.62823 γ + γ + B, 3B₄ 30.235 52.8404 γ + γ + B, 3B₄ 29.7518162.791 γ + γ + B, 3B₄ 29.3164 26.506 γ + γ + B, 3B₄ 27.5695 15.4471Bγ + B, 2B₂ 27.1341 59.1216 Bγ + B, 2B₂ 26.4811 8.58222 Bγ + B, 2B₂24.4475 5.93996 ββB 23.12 5.05181 2B₄ 22.6369 29.7047 2B₅+, 2 EOC20.1626 6.29481 2B₃ 19.7378 31.9342 1B₁ 19.2068 3.93019 1B₁ 14.25825.59441 1B₃ 13.8706 36.3938 1B₄+, 1 EOC 10.9768 9.89028 1B₂

Example 139

[1062] 1-Pentene (20 ml) was polymerized in 20 ml chloroform accordingto example 138 to give 2.59 g of viscous fluid (369 equivalents1-pentene per Pd). Integration of the ¹H NMR spectrum showed 118 methylcarbons per 1000 methylene carbons. DSC (two heats, 150 to +150° C., 15°C./min) shows Tg=−58° C. and a low temperature melting endotherm from−50° C. to 30° C. (32 J/g).

[1063]¹³C NMR quantitative analysis, branching per 1000 CH₂: Totalmethyls (118), Methyl (85.3), Ethyl (none detected), Propyl (15.6),Butyl (non detected), ≧Amyl and end of chains (17.1). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=22,500,M_(w)=43,800, M_(w)/M_(n)=1.94.

[1064] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity42.6277 4.69744 αα for Me & Et⁺ 39.5428 9.5323 3^(rd) carbon of a 6⁺carbon side chain that has a methyl branch at the 4 position 38.13573.59535 37.8384 13.9563 MB₃ ⁺ 37.5888 28.4579 37.2224 54.6811 αB₁, 3B₃35.5287 6.51708 35.2419 3.55603 34.6366 7.35366 34.2437 22.3787 32.91145.2064 MB₁ 32.5977 10.5375 32.38 4.02878 31.8809 14.1607 3B₆+, 3EOC30.6916 8.44427 γ⁺γ⁺B 30.0703 63.1613 γ⁺γ⁺B 29.6987 248 γ⁺γ⁺B 29.263317.9013 γ⁺γ⁺B 28.8916 3.60422 27.1182 66.2971 βγ⁺B, (4B₅, etc.) 24.532416.8854 22.5784 16.0395 2B₅+, 2EOC 20.1041 13.2742 19.6952 54.3903 1B₁,2B₃ 14.2104 12.2831 13.8281 16.8199 1B₄+, EOC, 1B₃

[1065] Integration of the CH₂ peaks due to the structure—CH(R)CH₂CH(R′)—, where R is an alkyl group, and R′ is an alkyl groupwith two or more carbons showed that in 69% of these structures, R═Me.The region integrated for the structure where both R and R′ are ≧Ethylwas 39.7 ppm to 41.9 ppm to avoid including an interference from anothertype of methylene carbon on a side chain.

Example 140

[1066] [(2,6-i-PrPh)₂DABMe₂]PdMeCl (0.020 g, 0.036 mmol) was dissolvedin 4 ml CH₂Cl₂ and methyl acrylate (0.162 g, 0.38 mmol, inhibited with50 ppm phenothiazine) was added while stirring. This solution was addedto a stirred suspension of NaBAF (0.033 g, 0.038 mmol) in 4 ml ofCH₂Cl₂. After stirring for 1 hour, the mixture was filtered through a0.5 μm PTFE membrane filter to remove a flocculant gray precipitate. Thesolvent was removed from the filtrate in vacuo to give a solid which wasrecrystallized from a CH₂Cl₂/pentane mixture at −40° C. to give 0.39 g(75% yield) of orange crystalline{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}BAF⁻. ¹H NMR (CDCl₃): 0.65(m,CH₂, 2H); 1.15-1.45(four sets of doublets for —CH(CH ₃)₂ and multipletat 1.4 for a CH₂, total area=26H); 2.19,2.21 (s,s, CH₃ of ligandbackbone, 6H); 2.40(m, CH₂, 2H); 2.90 (m, —CH(CH₃)₂, 4H); 3.05(s,—CO₂CH₃, 3H); 7.25-7.75(m, aromatic H of ligand and counterion, 19H).

[1067] All GPC data reported for examples 141-170, 177, and 204-212 wererun in trichlorobenzene vs. polyethylene standards unless otherwiseindicated. All DSC data reported for examples 141-170, 177, and 204-212(second heat, −150° C. to 150°, 10 or 15° C./min)

Example 141

[1068] A Schlenk flask containing {[(2,6-i-PrPh)₂DABH₂]NiMe(Et₂O)}BAF⁻(1.3 mg, 8.3×10⁻⁷ mol) under an argon atmosphere was cooled to −78° C.Upon cooling, the argon was evacuated and the flask backfilled withethylene (1 atm). Toluene (75 mL) was added via syringe. Thepolymerization mixture was then warmed to 0° C. The solution was stirredfor 30 minutes. Polymer began to precipitate from the solution withinminutes. After 30 minutes, the polymerization was terminated uponexposing the catalyst to air. The polymer was precipitated from acetone,collected by filtration and washed with 6 M HCl, water, and acetone. Thepolymer was dried in vacuo. The polymerization yielded 1.53 g ofpolyethylene (1.3×10⁵ TO). M_(n)=91,900; M_(w)=279,000;M_(w)/M_(n)=3.03; T_(m)=129° C. ¹H NMR (C₆D₅Cl, 142° C.) 0.6 methyls per100 carbons.

Example 142

[1069] The reaction was done in the same way as in Example 141 using 1.3mg of {[(2,6-i-PrPh)₂DABMe₂]NiMe(Et₂O)}BAF⁻ (8.3×10⁻⁷ mol). The polymerwas isolated as a white solid (0.1 g).

Examples 143-148

[1070] General procedure for the polymerization of ethylene by themethylaluminoxane (MAO) activation of nickel complexes containingbidentate diimine ligands: Polymerization at 0° C.: The bisimine nickeldihalide complex (1.7×10⁻⁵ mol) was combined with toluene (100 mL) in aflame dried Schlenk flask under 1 atmosphere ethylene pressure. Thepolymerization was cooled to 0° C. in an ice-water bath. The mixture wasstirred at 0° C. for 15 minutes prior to activation with MAO.Subsequently, 1.5 mL of a 10% MAO (100 eq) solution in toluene was addedonto the nickel dihalide suspension. The solution was stirred at 0° C.for 10, 30, or 60 minutes. Within minutes increased viscosity and/orprecipitation of polyethylene was observed. The polymerization wasquenched and the polymer precipitated from acetone. The polymer wascollected by suction filtration and dried under vacuum for 24 hours. SeeTable I for a detailed description of molecular weight and catalystactivity data. Example No. Catalyst 143 [(2,6-i-PrPh)₂DABH₂]NiBr₂ 144[(2,6-i-PrPh)₂DABMe₂]NiBr₂ 145 [(2,6-MePh)₂DABH₂]NiBr₂ 146[(2,6-i-PrPh)₂DABAn]NiBr₂ 147 [(2,6-MePh)₂DABAn]NiBr₂ 148[(2,6-MePh)₂DABMe₂]NiBr₂ TO/ Thermal Ex- Condi- Yield hr · mol Analysisam. tions¹ (g) catalyst M_(n) M_(w) M_(w)/M_(n) (° C.) 143 0° C., 5.322,700  80,900 231,000 2.85 119 (T_(m)) 30 m 144² 0° C., 3.8 16,300403,000 795,000 1.97 115 (T_(m)) 30 m 145³ 0° C., 3.4 14,300  42,900107,000 2.49 131 (T_(m)) 30 m 146² 0° C., 7.0 29,900 168,000 389,0002.31 107 (T_(m)) 30 m 147 0° C., 3.7 47,500 125,000 362,000 2.89 122(T_(m)) 10 m 148 0° C., 5.1 65,400 171,000 440,000 2.58 115 (T_(m)) 10 m

Examples 149-154

[1071] Polymerization at Ambient Temperature The general proceduredescribed for the MAO activation of the diimine nickel dihalides wasfollowed in the polymerizations detailed below, except allpolymerizations were run between 25-30° C. Example No. Catalyst 149[(2,6-i-PrPh)₂DABH₂]NiBr₂ 150 [(2,6-i-PrPh)₂DABMe₂]NiBr₂ 151[(2,6-MePh)₂DABH₂]NiBr₂ 152 [(2,6-i-PrPh)₂DABAn]NiBr₂ 153[(2,6-MePh)₂DABAn]NiBr₂ 154 [(2,6-MePh)₂DABMe₂]NiBr₂ TO/ Thermal Condi-Yield hr · mol M_(w)/ Analysis Exam. tions¹ (g) catalyst M_(n) M_(w)M_(n) (° C.) 149 30° C., 2.5 12,200  15,500  34,900 2.25 — 30 m 150² 25°C., 3.4 14,500 173,000 248,000 1.44 −51 (T_(g)) 30 m 151³ 25° C., 7.230,800  13,900  39,900 2.88 90,112 30 m (T_(m)) 152² 25° C., 4.2 18,000 82,300 175,000 2.80 39 (T_(m)) 30 m 153 25° C., 4.9 62,900  14,000 25,800 1.85 — 10 m 154 25° C., 3.7 47,500  20,000  36,000 1.83 — 10 m

Example 155

[1072] A standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂ was prepared asfollows: 1,2-difluorobenzene (10 mL) was added to 6.0 mg of[(2,6-i-PrPh)₂DABAn]NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask.The standard solution was transferred to a Kontes flask and stored underan argon atmosphere.

[1073] The standard catalyst solution (1.0 mL, 8.4×10⁻⁷ mol catalyst)was added to a Schlenk flask which contained 100 mL toluene, and wasunder 1 atmosphere ethylene pressure. The solution was cooled to 0° C.,and 1.5 mL of a 10% solution of MAO (≧1000 eq) was added. The solutionwas stirred for 30 minutes. Polymer began to precipitate within minutes.The polymerization was quenched and the polymer precipitated fromacetone. The resulting polymer was dried in vacuo (2.15 g, 1.84×10⁵ TO).M_(n)=489,000; M_(w)=1,200,000; M_(w)/M_(n)=2.47

Example 156

[1074] The polymerization of ethylene at 25° C. was accomplished in anidentical manner to that described in Example 155. The polymerizationyielded 1.8 g of polyethylene (1.53×10⁵ TO). M_(n)=190,000;M_(w)=410,000; M_(w)/M_(n)=2.16; ¹H NMR (C₆D₅Cl, 142° C.) 7 methyls per100 carbons.

Example 157

[1075] A standard solution of [(2,6-MePh)₂DABAn]NiBr₂ was prepared inthe same way as described for the complex in Example 155 using 5.0 mg of[(2,6-MePh)₂DABAn]NiBr₂ (8.4×10⁻⁶ mol).

[1076] Toluene (100 mL) and 1.0 mL of the standard solution of complex 5(8.3×10⁻⁷ mol catalyst) were combined in a Schlenk flask under 1atmosphere ethylene pressure. The solution was cooled to 0° C., and 1.5mL of a 10% solution of MAO(≧1000 eq) was added. The polymerizationmixture was stirred for 30 minutes. The polymerization was terminatedand the polymer precipitated from acetone. The reaction yielded 1.60 gof polyethylene (1.4×10⁵ TO). M_(n)=590,000; M_(w)=1,350,000;M_(w)/M_(n)=2.29.

Example 158

[1077] Toluene (200 mL) and 1.0 mL of a standard solution of[(2,6-i-PrPh)₂DABAn]NiBr₂ (8.3×10⁻⁷ mol catalyst) were combined in aFisher-Porter pressure vessel. The resulting solution was cooled to 0°C., and 1.0 mL of a 10% MAO (≧1000 eq) solution in toluene was added toactivate the polymerization. Subsequent to the MAO addition, the reactorwas rapidly pressurized to 276 kPa. The solution was stirred for 30minutes at 0° C. After 30 minutes, the reaction was quenched and polymerprecipitated from acetone. The resulting polymer was dried under reducedpressure. The polymerization yielded 2.13 g of white polyethylene(1.82×10⁵ TO). M_(n)=611,000; M_(w)=1,400,000; M_(w)/M_(n)=2.29;T_(m)=123° C.; ¹H NMR (C₆D₅Cl, 142° C.) 0.5 methyls per 100 carbons.

Examples 159-160

[1078] Polymerization of Propylene The diimine nickel dihalide complex(1.7×10⁻⁵ mol) was combined with toluene (100 mL) in a Schlenk flaskunder 1 atmosphere propylene pressure. The polymerization was cooled to0° C., and 1.5 mL of a 10% MAO (100 eq) solution in toluene was added.The solution was stirred for 2 hours. The polymerization was quenchedand the polymer precipitated from acetone. The polymer was dried undervacuum. Example No. Catalyst 159 [(2,6-i-PrPh)₂DABH₂]NiBr₂ 160[(2,6-i-PrPh)₂DABAn]NiBr₂ TO/ Thermal Ex- Condi- Yield hr · mol M_(w)/Analysis am. tions¹ (g) catalyst M_(n) M_(w) M_(n) (° C.) 159 0° C., 1.3900  131,000^(a) 226,000 1.72 −20 (T_(g)) 2 h 160 0° C., 4.3 2,900147,000 235,000 1.60 −78, −20 2 h (T_(g)) # δ⁺/γ (0.98).

[1079] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 140 C., 0.05M CrAcAc Freq ppm Intensity47.3161 53.1767 46.9816 89.3849 46.4188 82.4488 45.84 23.1784 38.470212.8395 38.0985 29.2643 37.472 18.6544 37.2915 24.8559 35.3747 15.697134.5623 14.6353 33.3145 14.2876 32.996 12.2454 30.9464 24.2132 30.670357.4826 30.081 30.122 γ to single branch 29.6987 29.2186 δ⁺ to branch28.3659 298.691 27.4792 33.2539 27.1235 29.7384 24.5324 9.45408 21.155420.0541 20.6244 110.077 19.9926 135.356 16.9342 8.67216 16.4829 8.8140414.9962 8.38097

Example 161

[1080] [(2,6-i-PrPh)₂DABH₂]NiBr₂ (10 mg, 1.7×10⁻⁵ mol) was combined withtoluene (40 mL) under a N₂ atmosphere. A 10% solution of MAO (1.5 mL,100 eq) was added to the solution. After 30 minutes, the Schlenk flaskwas backfilled with propylene. The reaction was stirred at roomtemperature for 5.5 hours. The polymerization was quenched, and theresulting polymer dried under vacuum (670 mg, 213 TO/h). M_(n)=176,000;M_(w)=299,000; M_(w)/M_(n)=1.70. Quantitative ¹³C NMR analysis,branching per 1000 CH₂: Total methyls (626), Methyl (501), Ethyl (1),≧Butyl and end of chain (7). Based on the total methyls, the fraction of1,3-enchainment is 22%. Analysis of backbone carbons (per 1000 CH₂): δ⁺(31), δ⁺/γ (0.76).

Examples 162-165

[1081] The diimine nickel dihalide catalyst precursor (1.7×10⁻⁵ mol) wascombined with toluene (40 mL) and 1-hexene (10 mL) under a N₂atmosphere. Polymerization reactions of 1-hexene were run at both 0° C.and room temperature. A 10% solution of MAO (1.5 mL, 100 eq) in toluenewas added. Typically the polymerization reactions were stirred for 1-2hours. The polymer was precipitated from acetone and collected bysuction filtration. The resulting polymer was dried under vacuum. Ex.No. Catalyst 162 [(2,6-i-PrPh)₂DABH₂]NiBr₂ 163 [(2,6-i-PrPh)₂DABAn]NiBr₂164 [(2,6-i-PrPh)₂DABH₂]NiBr₂ 165 [(2,6-i-PrPh)₂DABAn]NiBr₂ TO/ ThermalEx- Condi- Yield hr · mol M_(w)/ Analysis am. tions¹ (g) catalyst M_(n)^(a) M_(w) M_(n) (° C.) 162 25° C., 3.0 2100 173,000 318,000 1.84 −48(T_(g)) 1 h 163 25° C., 1.2 860 314,000 642,000 2.05 −54 (T_(g)) 1 h −19(T_(m)) 164 0° C., 3.0 1100 70,800 128,000 1.80 −45 (T_(g)) 2 h 165 0°C., 1.5 540 91,700 142,000 1.55 −49 (T_(g)) 2 h

[1082] ¹³C NMR data (Example 162) TCB, 120 C., 0.05M CrAcAc Freg ppmIntensity 42.8364 7.99519 Methine 41.3129 27.5914 αα to two Eth⁺branches 40.5759 19.6201 αα to two Eth⁺ branches 37.8831 14.7864Methines and Methylenes 37.2984 93.6984 Methines and Methylenes 36.66846.99225 Methines and Methylenes 35.5773 36.067 Methines and Methylenes34.655 55.825 Methines and Methylenes 34.3091 63.3862 Methines andMethylenes 33.8356 24.1992 Methines and Methylenes 33.428 53.7439Methines and Methylenes 32.9957 51.1648 Methines and Methylenes 31.916917.4373 Methines and Methylenes 31.5546 14.008 Methines and Methylenes31.1552 10.6667 Methines and Methylenes 30.5993 34.6931 Methines andMethylenes 30.274 56.8489 Methines and Methylenes 30.1258 42.1332Methines and Methylenes 29.747 97.9715 Methines and Methylenes 29.104747.1924 Methines and Methylenes 28.8823 64.5807 Methines and Methylenes28.1289 13.6645 Methines and Methylenes 27.5648 61.3977 Methines andMethylenes 27.1777 50.9087 Methines and Methylenes 27.0213 31.6159Methines and Methylenes 26.9142 31.9306 Methines and Methylenes 26.45724.715666 Methines and Methylenes 23.2085 154.844 2B₄ 22.6074 12.07192B₅+, EOC 20.0669 8.41495 1B₁ 19.6963 57.6935 1B₁ 15.9494 17.710814.3477 8.98123 13.8742 248 1B₄+, EOC

Example 166

[1083] [(2,6-i-PrPh)₂DABMe₂]NiBr₂ (10.4 mg, 1.7×10⁻⁵ mol) was combinedwith toluene (15 mL) and 1-hexene (40 mL) under 1 atmosphere ethylenepressure. The solution was cooled to 0° C., and 1.5 mL of a 10% MAO (100eq) solution in toluene was added. The reaction was stirred at 0° C. for2.5 hours. The polymerization was quenched and the polymer precipitatedfrom acetone. The resulting polymer was dried under reduced pressure(1.4 g). Mn=299,000; Mw=632,000; Mw/Mn=2.12.

[1084] Branching Analysis by ¹³C NMR per 1000 CH₂: Total methyls(101.3), Methyl (36.3), Ethyl (1.3), Propyl (6.8), Butyl (47.7), ≧Amyland end of chains (11.5).

Example 167

[1085] [(2,6-i-PrPh)₂DABH₂]NiBr₂ (10 mg, 1.7×10⁻⁵ mol) was added to asolution which contained toluene (30 mL) and 1-octene (20 mL) under 1atm ethylene. A 10% solution of MAO (1.5 mL, 100 eq) in toluene wasadded. The resulting purple solution was allowed to stir for 4 hours atroom temperature. Solution viscosity increased over the duration of thepolymerization. The polymer was precipitated from acetone and driedunder vacuum resulting in 5.3 g of copolymer. M_(n)=15,200,M_(w)=29,100, M_(n)/M_(w)=1.92.

Example 168

[1086] [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (75 mL) in a Schlenk flask under 1 atmosphere ethylene pressure.The mixture was cooled to 0° C., and 0.09 mL of a 1.8 M solution intoluene of Et₂AlCl (10 eq) was added. The resulting purple solution wasstirred for 30 minutes at 0° C. The polymerization was quenched and thepolymer precipitated from acetone. The resulting polymer was dried underreduced pressure (6.6 g, 2.8×10⁴ TO). M_(n)=105,000; M_(w)=232,000;M_(w)/M_(n)=2.21

Example 169

[1087] [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (75 mL) under 1 atmosphere propylene pressure. The solution wascooled to 0° C. and 0.1 mL of Et₂AlCl (≧10 eq) was added. The reactionwas stirred at 0° C. for 2 hours. The polymerization was quenched andthe polymer precipitated from acetone. The resulting polymer was driedunder reduced pressure (3.97 g, 2800 TO).

Example 170

[1088] [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (50 mL) and 1-hexene (25 mL) under a N₂ atmosphere. Et₂AlCl(0.01 mL, 10 eq) was added to the polymerization mixture. The resultingpurple solution was allowed to stir for 4 hours. After 4 hours thepolymerization was quenched and the polymer precipitated from acetone.The polymerization yielded 1.95 g poly(1-hexene) (348 TO/h).M_(n)=373,000; M_(w)=680,000; M_(w)/M_(n)=1.81.

Example 171

[1089] 1-Tetradecene (20 ml) was polymerized in methylene chloride (10ml) for 20 hr using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.04 g, 0.05 mmol).The solvent and reacted monomer were removed in vacuo. The polymer wasprecipitated to remove unreacted monomer, by the addition of acetone toa chloroform solution. The precipitated polymer was dried in vacuo togive a 10.2 g yield. ¹³C NMR (trichlorobenzene, 120° C.) integrated togive the following branching analysis per 1000 methylene carbons: Totalmethyls (69.9), methyl (24.5), ethyl (11.4), propyl (3.7), butyl (2.3)amyl (0.3), ≧Hexyl and end of chain (24.2). Thermal analysis showedTg=−42.7° C., and Tm=33.7° C. (15.2 J/g).

[1090] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity39.3416 7.78511 MB₂ 38.2329 5.03571 MB₃ _(⁺) 37.8616 9.01667 MB₃ _(⁺)37.5857 3.33517 MB₃ _(⁺) 37.2462 31.8174 αB₁, 3B₃ 36.6415 2.92585 αB₁,3B₃ 34.668 5.10337 αγ⁺B 34.2384 38.7927 αγ⁺B 33.7397 16.9614 3B₅ 33.34713.23743 3B₆+, 3EOC 32.9387 16.0951 γ⁺γ⁺B, 3B₄ 31.9148 27.6457 γ⁺γ⁺B, 3B₄31.1297 6.03301 γ⁺γ⁺B, 3B₄ 30.212 59.4286 γ⁺γ⁺B, 3B₄ 29.7398 317.201γ⁺γ⁺B, 3B₄ 29.3101 32.1392 γ⁺γ⁺B, 3B₄ 27.1511 46.0554 βγ⁺B, 2B₂ 27.018553.103 βγ⁺B, 2B₂ 26.419 9.8189 βγ⁺B, 2B₂ 24.244 2.46963 ββB 22.620728.924 2B₅+, 2EOC 20.0479 3.22712 2B₃ 19.7084 18.5679 1B₁ 14.39293.44368 1B₃ 13.8677 30.6056 1B₄+, 1EOC 10.9448 9.43801 1B₂

Example 172

[1091] 4-Methyl-1-pentene (20 ml) was polymerized in methylene chloride(10 ml) for 19 hr using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.04 g, 0.05 mmol).The solvent and unreacted monomer were removed in vacuo. The polymer wasprecipitated to remove residual monomer by addition of excess acetone toa chloroform solution. The precipitated polymer was dried in vacuo togive a 5.7 g yield. ¹³C NMR (trichlorobenzene, 120° C.) integrated togive 518 methyls per 1000 methylene carbon atoms. Thermal analysisshowed Tg −30.3° C.

[1092] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity47.8896 13.3323 47.4011 8.54293 45.7127 26.142 45.1392 17.4909 43.965813.9892 43.1375 12.7089 42.6171 11.5396 41.8207 9.00437 39.203 64.935737.9712 24.4318 37.3075 87.438 35.4862 16.3581 34.9553 24.5286 34.3531.8827 33.3624 25.7696 33.0226 42.2982 31.4403 25.3221 30.6226 38.708328.504 26.8149 27.989 81.8147 27.7341 78.3801 27.5802 94.6195 27.45875.8356 27.0864 35.5524 25.6103 97.0113 23.4333 59.6829 23.0563 41.571222.536 154.144 21.9944 5.33517 20.7307 16.294 20.4971 34.7892 20.295329.9359 19.7378 62.0082

Example 173

[1093] 1-Eicosene (19.0 g) was polymerized in methylene chloride (15 ml)for 24 hr using catalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆⁻ (0.047 g, 0.05 mmol). The solvent and unreacted monomer were removedin vacuo. The polymer was precipitated to remove residual monomer byaddition of excess acetone to a chloroform solution of the polymer. Thesolution was filtered to collect the polymer. The precipitated polymerwas dried in vacuo to give a 5.0 g yield. ¹³C NMR quantitative analysis,branching per 1000 CH2: Total methyls (27), Methyl (14.3), Ethyl (0),Propyl (0.2), Butyl (0.6), Amyl (0.4), ≧Hexyl and end of chains (12.4).

[1094] Integration of the CH₂ peaks due to the structure—CH(R)CH₂CH(R′)—, where R is an alkyl group, and R′ is an alkyl groupwith two or more carbons showed that in 82% of these structures, R═Me.

[1095] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data (Example 162) TCB, 120 C., 0.05M CrAcAc Freq ppmIntensity 37.7853 13.978 MB₂ ⁺ 37.1428 52.1332 αB 34.1588 41.067 αB₄ ⁺32.826 26.6707 MB₁ 31.8066 24.9262 3B₆ ⁺, 3EOC 30.0703 96.4154 γ⁺γ⁺B,3B₄ 29.6243 1239.8 γ⁺γ⁺B, 3B₄ 27.0013 78.7094 Bγ⁺B, (4B₅, etc.) 22.504123.2209 2B₅ ⁺, 2EOC 19.605 30.1221 1B₁ 13.759 23.5115 1B₄ ⁺, EOC

Example 174

[1096] The complex [(2,6-i-PrPh)₂DABH₂]PdMeCl (0.010 g, 0.019 mmol) andnorbornene (0.882 g, 9.37 mmol) were weighed into a vial and dissolvedin 2 ml CH₂Cl₂. NaBAF (0.032 g, 0.036 mmol) was rinsed into the stirringmixture with 2 ml of CH₂Cl₂ After stirring about 5 minutes, there wassudden formation of a solid precipitate. Four ml of o-dichlorobenzenewas added and the solution became homogenous and slightly viscous. Afterstirring for 3 days, the homogeneous orange solution was moderatelyviscous. The polymer was precipitated by addition of the solution toexcess MeOH, isolated by filtration, and dried in vacuo to give 0.285 g(160 equivalents norbornene per Pd) bright orange glassy solid. DSC (twoheats, 15° C./min) showed no thermal events from −50 to 300° C. This isconsistent with addition type poly(norbornene). Ring-openingpolymerization of norbornene is known to produce an amorphous polymerwith a glass transition temperature of about 30-55° C.

Example 175

[1097] The solid complex {[(2,6-i-PrPh)₂DABH₂]PdMe(Et₂O)}SbF₆ ⁻ (0.080g, 0.10 mmol) was added as a solid to a stirring solution of norbornene(1.865 g) in 20 ml of o-dichlorobenzene in the drybox. About 30 minafter the start of the reaction, there was slight viscosity (foam onshaking) and the homogeneous mixture was dark orange/red. After stirringfor 20 h, the solvent and unreacted norbornene were removed in vacuo togive 0.508 g orange-red glassy solid (54 equivalents norbornene/Pd). ¹HNMR (CDCl₃): broad featureless peaks from 0.8-2.4 ppm, no peaks in theolefinic region. This spectrum is consistent with addition typepoly(norbornene). GPC (trichlorobenzene, 135° C., polystyrene reference,results calculated as linear polyethylene using universal calibrationtheory): Mn=566 Mw=1640 Mw/Mn=2.90.

Example 176

[1098] 4-Methyl-1-pentene (10 ml) and ethylene (1 atm) werecopolymerized in 30 ml of chloroform according to example 125 usingcatalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.084 g, 0.10mmol) to give 23.29 g highly viscous yellow oil. The ¹H NMR spectrum wassimilar to the poly(ethylene) of example 110 with 117 methyl carbons per1000 methylene carbons. ¹³C NMR quantitative analysis, branching per1000 CH₂: Total methyls (117.1), Methyl (41.5), Ethyl (22.7), Propyl(3.3), Butyl (13), Amyl (1.2), ≧Hexyl and end of chains (33.1), ≧Amyland end of chains (42.3), By ¹³C NMR this sample contains twoidentifiable branches at low levels attributable to 4-methyl-1-pentene.The Bu and ≧Amyl peaks contain small contributions from isopropyl endedbranch structures.

Example 177

[1099] CoCl₂ (500 mg, 3.85 mmol) and (2,6-i-PrPh)₂DABAn (2.0 g, 4.0mmol) were combined as solids and dissolved in 50 mL of THF. The brownsolution was stirred for 4 hours at 25° C. The solvent was removed underreduced pressure resulting in a brown solid (1.97 g, 82% yield).

[1100] A portion of the brown solid (12 mg) was immediately transferredto another Schlenk flask and dissolved in 50 mL of toluene under 1atmosphere of ethylene. The solution was cooled to 0° C., and 1.5 mL ofa 10% MAO solution in toluene was added. The resulting purple solutionwas warmed to 25° C. and stirred for 12 hours. The polymerization wasquenched and the polymer precipitated from acetone. The white polymer(200 mg) was collected by filtration and dried under reduced pressure.M_(n)=225,000, M_(w)=519,000, M_(w)/M_(n)=2.31, T_(g)=−42°, T_(m)=52° C.and 99.7° C.

Example 178

[1101] Ethyl 10-undecenoate (10 ml) and ethylene (1 atm) werecopolymerized in 30 ml of CH₂Cl₂ according to example 125 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻ (0.084 g, 0.10 mmol).The copolymer was precipitated by removing most of the CH₂Cl₂ in vacuo,followed by addition of excess acetone. The solution was decanted andthe copolymer was dried in vacuo to give 1.35 g viscous fluid. ¹H NMR(CDCl₃): 0.75-0.95(m, CH₃); 0.95-1.5(m, —C(O)OCH2CH ₃, CH₂, CH);1.5-1.7(m, —CH ₂CH₂C(O)OCH₂CH₃); 1.9-2.0(m, —CH ₂CH═CH—); 2.3(t, —CH₂CH₂C(O)OCH₂CH₃); 4.15(q, —CH₂CH₂C(O)OCH ₂CH₃); 5.40(m, —CH═CH—). Theolefinic and allylic peaks are due to isomerized ethyl 10-undecenoatewhich has coprecipitated with the copolymer. Adjusting for this, theactual weight of copolymer in this sample is 1.18 g. The copolymer wasreprecipitated by addition of excess acetone to a chloroform solution.¹H NMR of the reprecipitated polymer is similar except there are nopeaks due to isomerized ethyl 10-undecenoate at 1.9-2.0 and 5.40 ppm.Based on integration, the reprecipitated copolymer contains 7.4 mole %ethyl 10-undecenoate, and 83 methyl carbons per 1000 methylene carbons.¹³C NMR quantitative analysis, branching per 1000 CH²: Total methyls(84.5), Methyl (31.7), Ethyl( 16.9), Propyl (1.5), Butyl (7.8), Amyl(4.4), ≧Hexyl and end of chains (22.3). GPC (THF, PMMA standard):Mn=20,300 Mw=26,300 Mw/Mn=1.30. ¹³C NMR quantitative analysis, branchingper 1000 CH2: ethyl ester (37.8), Ester branches —CH(CH₂)nCO₂CH₂CH₃ as a% of total ester: n≧5 (65.8), n=4 (6.5), n=1,2,3 (26.5), n=0 (1.2).

[1102] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data Freq ppm Intensity 59.5337 53.217 39.7234 2.5736139.3145 7.80953 38.2207 11.9395 37.8437 20.3066 37.2225 29.7808 36.71815.22075 34.6792 17.6322 34.265 107.55 33.7181 21.9369 33.3093 8.2257432.9164 15.0995 32.396 8.52655 32.0828 5.79098 31.9075 37.468 31.12713.8003 30.6757 8.38026 30.2084 52.5908 29.9961 27.3761 29.72 151.16429.5076 39.2815 29.2899 69.7714 28.727 6.50082 27.5164 20.4174 26.990864.4298 26.5713 9.18236 26.3749 11.8136 25.5519 4.52152 25.0528 43.755424.2457 7.9589 23.1094 10.0537 22.9926 4.71618 22.6156 37.2966 20.02452.4263 19.6847 25.9312 19.1643 5.33693 17.5183 2.20778 14.2954 66.175913.8653 43.8215 13.414 2.52882 11.1521 5.9183 10.9237 14.9294 174.9453.27848 172.184 125.486 171.695 4.57235

Example 179

[1103] The solid complex {[(2,6-i-PrPh)₂DABH₂]PdMe(Et₂O)}SbF₆ ⁻ (0.080g, 0.10 mmol) was added as a solid to a stirring solution ofcyclopentene (1.35 g, 20 mmol) in 20 ml of dichlorobenzene in thedrybox. After stirring 20 h, the slightly viscous solution was worked upby removing the solvent in vacuo to give 1.05 g sticky solid (156equivalents of cyclopentene per Pd). ¹H NMR (CDCl₃): complex spectrumfrom 0.6-2.6 ppm with maxima at 0.75, 1.05, 1.20, 1.55, 1.65, 1.85,2.10, 2.25, and 2.50. There is also a multiplet for internal olefin at5.25-5.35. This is consistent with a trisubstituted cyclopentenyl endgroup with a single proton (W. M. Kelly et. al., Macromolecules 1994,27, 4477-4485.) Integration assuming one olefinic proton per polymerchain gives DP=8.0 and Mn=540. IR (Thin film between NaCl plates, cm⁻¹):3048 (vw, olefinic end group, CH stretch), 1646(vw, olefinic end group,R₂C═CHR trisubstituted double bond stretch), 1464(vs), 1447(vs),1364(m), 1332(m), 1257(w), 1035(w), 946(m), 895(w), 882(w), 803(m,cyclopentenyl end group, R₂C═CHR trisubstituted double bond, CH bend),721(vw, cyclopentenyl end group, RHC═CHR disubstituted double bond, CHbend). GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):M_(n)=138 M=246 M_(w)/M_(n)=1.79.

Example 180

[1104] The solid complex {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆⁻ (0.084 g, 0.10 mmol) was added to a stirring solution of 10.0 mlcyclopentene in 10 ml CHCl₃ in the drybox. After stirring for 20 h, themixture appeared to be separated into two phases. The solvent andunreacted monomer were removed in vacuo leaving 2.20 g off-white solid(323 equivalents cyclopentene per Pd). DSC (25 to 300° C., 15° C./min,first heat): Tg=107° C., Tm (onset)=165° C., Tm (end)=260° C., Heat offusion=29 J/g.

[1105] Similar results were obtained on the second heat. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=28,700M_(w)=33,300 M_(w)/M_(n)=1.16.

[1106] Listed below are the ¹³C NMR analysis for this polymer. ¹³C NMRdata TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity 46.4873 142.424 38.33959.7617 30.5886 137.551

Example 181

[1107] The solid complex {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆⁻ (0.084 g, 0.10 mmol) was added to a stirring solution of 10.0 mlcyclopentene in 10 ml CHCl₃ in a Schlenk flask. The flask was evacuatedbriefly and refilled with ethylene. It was maintained under slightlyabove 1 atm ethylene pressure using a mercury bubbler. After 20 h, thesolvent and unreacted monomers were removed in vacuo from thehomogeneous solution to give 12.89 g of highly viscous fluid. ¹H-NMR(CDCl₃): cyclopentene peaks: 0.65(m, 1H); 1.15( broad s, 2H); 1.5-2.0(m,5H); ethylene peaks: 0.75-0.95(m, CH₃); 0.95-1.5(m, CH and CH₂).Integration shows 24 mole % cyclopentene in this copolymer. Analysis ofthe polyethylene part of the spectrum (omitting peaks due to cyclopentylunits) shows 75 total methyl carbons per 1000 methylene carbons. Basedon quantitative ¹³C analysis, the distribution of branches per 1000methylene carbons is Methyl (21), Ethyl (13), Propyl (˜0), Butyl (20)and ≧Amyl (20). DSC (first heat: 25 to 150° C., 10° C./min; first cool:150 to −150° C., 10° C./min; second heat: -150 to 150° C., 10° C./min,;values of second heat reported): Tg=−33° C., Tm=19° C. (11 J/g). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n)=3,960M_(w)=10,800 M_(w)/M_(n)=2.73.

[1108] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR Data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity48.344 1.85262 46.5562 22.8938 1 cme and/or 1,3 ccmcc 44.9064 10.80031,3 cme 42.0842 16.824 40.7845 117.364 2 eme 40.5777 113.702 1,3 eme40.3336 136.742 1,3 eme 39.5591 15.0962 methylene from 2 cmc or/and 2cme 38.7634 18.636 38.4716 12.3847 38.2488 17.3939 37.2144 17.583736.721 111.057 36.2913 11.0136 35.8776 22.0367 35.6176 90.3685 34.524815.734 34.1959 24.7661 33.0182 14.0261 31.8671 238.301 31.4056 20.640130.8433 11.2412 30.4613 20.2901 30.0104 62.2997 29.7133 78.3272 29.235931.6111 28.9653 53.5526 28.6577 64.0528 26.9813 17.6335 26.3925 4.5120825.9363 5.6969 24.2971 1.70709 22.9019 9.13305 2B₄ 22.6048 14.3641 2B₅+,2EOC 19.7349 10.124 1B₁ 19.1991 2.00384 1B₁ 17.5811 2.28331 end group13.8783 26.3448 1B₄+, 1EOC 12.6264 19.6468 end group 10.9501 4.96188 1B₂

Example 182

[1109] 1-Pentene (10 ml) and cyclopentene (10 ml) were copolymerized in20 ml of o-dichlorobenzene solvent according to example 180. After 72 h,the unreacted monomers and part of the solvent were removed in vacuo togive 3.75 g highly viscous fluid. Analysis by ¹H NMR showed that thismaterial contained 1.81 g of copolymer; the remainder waso-dichlorobenzene. The ¹H NMR spectrum was very similar topoly(ethylene-cocyclopentene) in Example 181. Integration shows 35 mole% cyclopentene in this copolymer. Analysis of the poly(1-pentene) partof the spectrum (omitting peaks due to cyclopentyl units) shows 62methyl carbons per 1000 methylene carbons. The fraction ofω,1-enchainment (chain straightening) in this section is 72%. Based onquantitative ¹³C analysis, the distribution of branches per 1000methylene carbons is Methyl (36), Propyl (7), and ≧Amyl (20). DSC (firstheat: −150 to 150° C., 15° C./min; first cool: 150 to −150° C., 15°C./min; second heat: −150 to 150° C., 15° C./min,; values of second heatreported): Tg=−19° C., Tm=50° C. (24 J/g). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as linear polyethyleneusing universal calibration theory): Mn=14,900 Mw=27,300 Mw/Mn=1.82

Example 183

[1110] A 100 mL autoclave was charged with chloroform (40 mL), methylacrylate (10 mL), {[(2,6-EtPh)₂DABMe₂]PdMe(NCMe)}BAF⁻ (0.100 g, 0.073mmol), and ethylene (2.1 MPa). The reaction mixture was stirred under1.4 MPa of ethylene for 180 min; during this time the temperature insidethe reactor remained between 25 and 26° C. The ethylene pressure wasthen vented, and the crude reaction mixture discharged from the reactor.The reactor was washed with 2×50 mL of chloroform. The washings wereadded to the crude reaction mixture; 250 mL of methanol was added to theresulting solution. After standing overnight, the polymer product hadprecipitated from solution; it was isolated by decanting off thechloroform/methanol solution, and dried giving 3.91 g of an extremelyviscous oil. ¹H NMR of this material showed it to be ethylene/methylacrylate copolymer, containing 1.1 mole % methyl acrylate. The polymercontained 128 methyl-ended hydrocarbon branches per 1000 methylenes, and7 methyl ester ended branches per 1000 methylenes.

Example 184

[1111] A solution of {[(Np)₂DABMe₂]PdMe(NCMe)}SbF₆ ⁻ (0.027 g, 0.02mmol) in 5 mL CDCl₃ was agitated under 1.4 MPa of ethylene for 3 h;during this time the temperature inside the reactor varied between 25and 40° C. ¹H NMR of the solution indicated the presence of ethyleneoligomers. Mn was calculated on the basis of ¹H NMR integration ofaliphatic vs. olefinic resonances to be 100. The degree ofpolymerization, DP, was calculated on the basis of the ¹H NMR spectrumto be 3.8; for a linear polymer this would result in 500 methyl-endedbranches per 1000 methylenes. However, based on the ¹H NMR spectrum thenumber of methyl-ended branches per 1000 methylenes was calculated to be787.

Example 185 [(2-t-BuPh)₂DABMe₂]NiBr₂

[1112] A Schlenk tube was charged with 0.288 g (0.826 mmol) of(2-t-BuPh)₂DABMe₂, which was then dissolved in 15 mL of CH₂Cl₂. Thissolution was cannulated onto a suspension of (DME)NiBr₂ (0.251 g, 0.813mmol) in 15 mL of CH₂Cl₂. The reaction mixture was allowed to stirovernight, resulting in a deep red solution. The solution was filteredand the solvent evaporated under vacuum. The remaining orange, oilyresidue was washed with ether (2×10 mL) and dried under vacuum to givean orange/rust powder (0.36 g, 78%).

Example 186 [(2-t-BuPh)₂DABAn]NiBr₂

[1113] (2-t-BuPh)₂DABAn (0.202 g, 0.454 mmol) and (DME)NiBr₂ (0.135 g,0.437 mmol) were combined and stirred in 25 mL of CH₂Cl₂, as in Example185. An orange/rust solid was isolated (0.18 g, 62%).

Example 187 [(2,5-t-BuPh)₂DABAn]NiBr₂

[1114] The corresponding diimine (0.559 g, 1.00 mmol) and (DME)NiBr₂(0.310 g, 1.00 mmol) were combined and stirred in 35 mL of CH₂Cl₂, aswas done in Example 185. An orange solid was isolated (0.64 g, 83%).

Examples 188-190

[1115] Polymerizations were carried out at 0° C. and under 1 atmosphereof ethylene pressure. The (diimine)NiBr₂ complex (1.4-1.7×10⁻⁵ mol) wasplaced into a flame-dried Schlenk flask and dissolved in 100 mL oftoluene. The flask was placed under ethylene and cooled in an ice bath.Polymerization was initiated by addition of 100 equivalents (1.5 mL 10%soln in toluene) of methylaluminoxane (MAO). The reaction mixture wasstirred for 30 or 120 minutes at constant temperature followed byquenching with 6M HCl. Polymer was precipitated from the resultingviscous solution with acetone, collected via filtration, and dried undervacuum for 24 h. A summary of results is shown below. Ex No. Catalyst188 [(2-t-BuPh)₂DABMe₂]NiBr₂ 189 [(2-t-BuPh)₂DABAn]NiBr₂ 190[(2,5-t-BuPh)₂DABAn]NiBr₂ Catalyst Yield TO/hr · mol Exam. (10⁻⁵ mol)Conditions (g) catalyst 188 (1.7) ° C., 120 m 9.88 10,500 189 (1.4) °C., 30 m 8.13 40,500 190 (1.5) ° C., 30 m 6.60 31,000

Examples 191-196

[1116] General Procedure. The procedure of Example 84 for thehomopolymerization of ethylene) was followed with the exception that theacrylate was added to the reaction mixture at −78° C. immediatelyfollowing the addition of 50 mL of CH₂Cl₂. Polymerizations are at roomtemperature (rt) and 1 atm ethylene unless stated otherwise. Thecopolymers were generally purified by filtering an Et₂O or petroleumether solution of the polymer through Celite and/or neutral alumina. ¹Hand ¹³C NMR spectroscopic data and GPC analysis are consistent with theformation of random copolymers. In addition to the polyethyleneresonances, the following resonances diagnostic of acrylateincorporation were observed:

[1117] Methyl Acrylate: ¹H NMR (CDCl₃, 400 MHz) δ3.64 (s, OMe), 2.28 (t,J=7.48, OCH₂), 1.58 (m, OCH₂CH₂); ¹³C NMR (C₆D₆, 100 MHz) δ176 (C(O)),50.9 (C(O)OMe).

[1118] Fluorinated Octyl Acrylate (FOA, 3M Co. Minneapolis, Minn.): ¹HNMR (CDCl₃, 400 MHz) δ4.58 (t, J=13.51, OCH₂(CF₂)₆CF₃), 2.40 (t, J=7.32,C(O)CH₂), 1.64 (m, C(O)CH₂CH₂); ¹³C NMR (CDCl₃, 100 MHz) δ172.1 (C(O)),59.3 (t, J_(CF)=27.0, OCH₂(CF₂)₆CF₃). Catalyst % (R), Acrylate conc.Acrylate, Rxn Inc. # CH₃/ (10⁻³ conc. Time Yield mol %/ 1000 Ex. Molar)(Molar) (h) (g) wt % CH₂ M_(w) M_(n) PDI 191 Me, 2.3 0 Me, 6.7  ²⁴ ^(a)≈0.5 10.9/27.3 134 192 Me, 1.4 0 Me, 1.1 48 3.94  2.7/7.84 114 7700056400 1.4^(b) 193 Me, 2.0 FOA, .74 24 27.5 0.80/11.58 110 194 Me, 2.0FOA, 1.3 24 20.7 0.80/11.58 126 195 H, 2.0 FOA, .74 24 1.49 0.31/4.85144 196 2.0^(C) FOA, .74 24 2.00 0.71/10.73 135

Examples 197-203

[1119] In Examples 197-203, structures of the type represented by (VI)and (IX) are described.

Example 197 {[(2.6-i-PrPh)₂DABMe₂]PdMe(H₂C═CH₂)}BAF⁻ and{[(2.6-i-PrPh)₂DABMe₂]Pd(P)H₂C═CH₂)}BAF⁻

[1120] In a drybox under an argon atmosphere, an NMR tube was chargedwith ˜0.01 mmol of<{[(2,6-i-PrPh)₂DABMe₂]PdMe}₂(μ-Cl)>BAF⁻/[(Na(OEt₂)₂BAF or NaBAF] or{[(2,6-i-PrPh)₂DABMe₂]PdMe(OEt₂)}BAF⁻. The tube was then capped with aseptum, removed from the drybox, and cooled to −78° C. Via gastightsyringe, 700 μL of CD₂Cl₂ was then added to the NMR tube and the septumwas wrapped with Parafilm. The tube was shaken very briefly in order todissolve the palladium complex. After acquiring a spectrum at −80° C.,1-10 equiv of olefin was added to the −78° C. solution via gastightsyringe, ant the olefin was dissolved in the solution by briefly shakingthe NMR tube. The tube was then transferred to the cold NMR probe andspectra were acquired. This olefin complex was prepared from bothprecursors using one equiv of ethylene: ¹H NMR (CD₂Cl₂, 400 MHz, −60°C.) δ7.72 (s, 8, BAF: C_(o)), 7.54 (s, 4, BAF: C_(p)), 7.4-7.0 (m, 6,H_(aryl)), 4.40 (s, 4, H₂C═CH₂), 3.38 (br m, 4, O(CH₂CH₃)₂), 2.69(septet, 2, J=6.73, CHMe₂), 2.63 (septet, 2, J=6.80, C′HMe₂), 2.34 and2.23 (s, 3 each, N═C(Me)—C′(Me)═N), 1.33 (d, 6, J=6.80, C′HMeMe′), 1.25(d, 6, J=6.50, CHMeMe′), 1.14 (d, 6, J=7.00, CHMeMe′), 1.10 (br m, 6,O(CH₂CH₃)₂), 1.07 (d, 6, J=6.80, C′HMeMe′), 0.18 (PdMe); ¹³C NMR(CD₂Cl₂, 100 MHz, −60° C.) δ180.3 and 174.7 (N═C—C′═N), 161.5 (q,J_(BC)=49.6, BAF: C_(ipso)) 143.3 and 141.7 (Ar, Ar′: C_(ipso)) 134.4(BAF: C_(o)), 128.6 (Ar: C_(p)), 128.4 (q, J_(BC)=32.3, BAF: C_(m)),127.7 (Ar′: C_(p)), 124.7 and 124.4 (Ar, Ar′: C_(o)), 117.3 (BAF:C_(p)), 91.7 (J_(CH)=160.7, H₂C═CH₂), 65.8 (O(CH₂CH₃)₂), 28.9 (CHMe₂),28.8 (C′HMe₂), 24.1, 23.4, 22.9 and 22.7 (CHMeMe′, C′HMeMe′), 21.7 and21.5 (N═C(Me)═C′(Me)═N), 15.0 (OCH₂CH₃)₂), 4.3 (PdMe).

[1121] In the presence of 5 equiv of ethylene, chain growth was observedat −35° C. Spectral data for {[(2,6-i-PrPh)₂DABMe₂]Pd(P)(CH₂═CH₂)}BAF⁻[wherein P is as defined for (VI)] intermediates (CD₂Cl₂, 400 MHz, −35°C.) are reported in the following table:{[(2,6-i-PrPh)₂DABMe₂]Pd[(CH₂)_(n)CH₃](H₂C═CH₂)}⁺BAF⁻ H₂C═CH₂N═C(Me)—C′(Me)═N Pd(CH₂)_(n)Me n mult. δ mult. δ mult. δ mult J δ 0 s4.42 s 2.35 s 2.24 s 0.22 2 s 4.36 s 2.37 s 2.22 t 7.00 0.39 4 s 4.36 s2.37 s 2.22 t 7.20 0.62

[1122] Addition of 15 more equiv of ethylene and warming to roomtemperature leads to complete consumption of ethylene and the observanceof a single organometallic species: ¹H NMR (CD₂Cl₂, 400 MHz, 24.0° C.)δ7.74 (s, 8, BAF: C_(o)), 7.19 (s, 4, BAF: H_(p)), 2.85 (br m, 4, CHMe₂,C′HMe₂), 2.36 and 2.23 (s, 3 each, N═C(Me)—C′(Me)═N), 1.5-1.0 (CHMeMe′,C′HMeMe′), 1.29 (Pd(CH₂)_(n)CH₃), 0.89 (Pd(CH₂)_(n)CH₃).

Example 198 {[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CH₂)}BAF⁻ and{[(2,6-i-PrPh)₂DABH₂]Pd(P)(H₂C═CH₂)}BAF⁻

[1123] This olefin complex, {[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CH₂)}BAF⁻, wasprepared following the procedure of example 197 by both of the analogoussynthetic routes used in example 197, using one equiv of ethylene: ¹HNMR (CD₂Cl₂, 400 MHz, −60° C.) δ8.42 and 8.26 (s, 1 each,N═C(H)—C′(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.54 (s, 4, BAF: H_(p)),7.42-7.29 (m, 6, H_(aryl)), 4.60 (s, H₂C═CH₂), 3.37 (q, 4, J=7.03,(O(CH₂CH₃)₂), 2.89 (septet, 2, J=6.71, CHMe₂), 2.76 (septet, 2, J=6.68,C′HMe₂), 1.35 (d, 6, J=6.72, C′HMeMe′), 1.29 (d, 6, J=6.79, CHMeMe′),1.15 (d, 6, J=6.72,CHMeMe′), 1.09 (d, 6, J=6.54, C′HMeMe′), 1.15 (t, 6,J=7.34, O(CH₂CH₃)₂), 0.46 (s, 3, PdMe); ¹³C NMR (CD₂Cl₂, 400 MHz, −60°C.) δ167.7 (J_(CH)=182, N═C(H)), 162.8 (J_(CH)=182, N═C′(H)), 161.4 (q,J=49.8, BAF: C_(ipso)), 140.2 and 139.8 (Ar, Ar′: C_(ipso)) 138.6 and137.3 (Ar, Ar′: C_(o)), 134.4 (BAF: C_(o)), 129.2 and 129.1 (Ar, Ar′:C_(p)), 128.3 (q, J_(CF)=32.2, BAF: C_(m)), 124.3 and 124.0 (Ar, Ar′:C_(m)), 124.2 (q, J_(CF)=272.5; BAF: CF₃), 117.3 (BAF: C_(p)), 92.7(J_(CH)=162.5, H₂C═CH₂), 65.8 (O(CH₂CH₃)₂), 28.9 and 28.7 (CHMe₂ andC′HMe₂), 25.1, 24.0, 22.0 and 21.9 (CHMeMe′, C′HMeMe′), 15.12(J_(CH)=139.2, PdMe), 15.09 (O(CH₂CH₃)₂).

[1124] In the presence of 10 equiv of ′ethylene, chain growth wasmonitored at −35° C. Diagnostic ¹H NMR spectral data (CD₂Cl₂, 400 MHz,−35° C.) for the second title compound are reported in the followingtable: {[(2,6-i-PrPh)₂DABH₂]Pd[(CH₂)_(n)CH₃](H₂C═CH₂)}⁺BAF⁻N═C(H)—C′(H)═N H₂C═CH₂ Pd(CH₂)_(n)Me n mult. δ mult. δ mult. δ mult J δ ⁰ ^(a) s 8.42 s 8.27 br s 4.6 s 0.50  ² ^(b) s 8.41 s 8.24 br s 4.6 t7.85 0.36 4 s 8.41 s 8.24 br s 4.6 t 7.15 0.62 6 s 8.41 s 8.24 br s 4.6t 7.25 0.76 >6   s 8.41 s 8.24 br s^(c) 4.6 m 0.85^(d)

[1125] After the ethylene was consumed at −35° C., the sample was cooledto −95° C. Broad upfield multiplets were observed at −7.2 to −7.5 ppmand −8.0 to −8.5 ppm. The sample was then warmed to room temperature anda spectrum was acquired. No olefins were detected, the upfieldmultiplets were no longer observable, and a single organometallicspecies was present: ¹H NMR (CD₂Cl₂, 400 MHz, 19.8° C.) δ8.41 and 8.28(s, 1 each, N═C(H)—C′(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.56 (s, 4, BAF:H_(p)), 3.09 (m, 4, CHMe₂, C′HMe₂), 1.35, 1.32, 1.26 and 1.22 (d, 6each, J=6.5-6.8, CHMeMe′, C′HMeMe′), 1.27 (Pd(CH₂)_(n)CH₃), 0.88(Pd(CH₂)_(n)CH₃).

[1126] A second spectrum was acquired 12 minutes later at roomtemperature. Substantial decomposition of the organometallic species wasobserved.

Example 199 {[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CH₂)}BAF⁻

[1127] This olefin complex, {([(2,6-MePh)₂DABH₂]PdMe(H₂C═CH₂)}BAF⁻, wasprepared following the procedure in example 197, using{[(2,6-MePh)₂DABH₂]PdMe(OEt₂)}BAF⁻ and one equiv of ethylene:

[1128]¹H NMR (CD₂Cl₂, 300 MHz, −70° C.) δ8.46 and 8.31 (s, 1 each,N═C(H)—C′(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.52 (s, 4, BAF: H_(p)),7.4-6.4 (m, 6, H_(aryl)), 4.56 (s, 4, H₂C═CH₂), 2.19 and 2.16 (s, 6each, Ar, Ar′: Me), 0.31 (s, 3, PdMe).

[1129] In the presence of 10 equiv of ethylene (eq 3), olefin insertionwas monitored at −30° C. and the production of cis- and trans-2-buteneswas observed.

Example 200 {[(2,6-i-PrPh)₂DABMe₂]PdMe(H₂C═CHMe)}BAF⁻

[1130] This olefin complex, {[(2,6-i-PrPh)₂DABMe₂]PdMe(H₂C═CHMe)}BAF,was prepared following the procedure of Example 197, using{[(2,6-i-PrPh)₂DABMe₂]PdMe(OEt₂)}BAF⁻ and one equiv of propylene:

[1131]¹H NMR (CD₂Cl₂, 400 MHz, −61° C.) δ7.73 (s, 8, BAF: H_(o)), 7.55(s, 4, BAF: H_(p)), 7.4-7.0 (m, 6, H_(aryl)), 5.00 (m, 1 H₂C═CHMe), 4.24(d, 1, J=9.1, HH′C═CHMe), 4.23 (d, 1, J=14.8, HH′C═CHMe), 3.38 (br q, 4,J=6.50, O(CH₂CH₃)₂), 2.84 (septet, 1, J=6.5, Ar: CHMe₂), 2.68 (m, 3, Ar:C′HMe₂; Ar′: CHMe₂, C′HMe₂), 2.32 and 2.22 (s, 3 each,N═C(Me)—C′(Me)═N), 1.63 (d, 3, J=6.40, H₂C═CHMe), 1.35, 1.30, 1.25, 1.1,1.1, 1.04 (d, 3 each, J=6.4-6.7, Ar: C′HMeMe′; Ar′: CHMeMe′, C′HMeMe′),1.24 and 1.1 (d, 3 each, J=6.4, Ar: CHMeMe′), 1.1 (m, 6, O(CH₂CH₃)₂),0.28 (PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz, −61° C.) δ179.9 and 174.7(N═C—C′═N), 161.5 (q, J_(BC)=49.7, BAF: C_(ipso)), 138.8, 137.9, 137.8,137.7, 137.0 and 136.9 (Ar: C_(ipso), C_(o), C_(o)′; Ar′: C_(ipso),C_(o), C_(o)′); 134.4 (BAF: C_(o)), 128.6 and 128.5 (Ar: C_(p), C_(p)′),128.4 (q, J_(CF)=31.6, BAF: C_(m)), 124.8, 124.7, 124.4 and 124.4 (Ar:C_(m), C_(m)′; Ar′: C_(m), C_(m)′), 124.2 (q, J_(CF)=272.5, BAF: CF₃),117.3 (BAF: C_(p)), 116.1 (J_(CH)=155.8, H₂C═CHMe), 85.6 (J_(CH)=161.4,H₂C═CHMe), 65.8 (O(CH₂CH₃)₂), 28.9, 28.7, 28.7, 28.7 (Ar: CHMe₂, C′HMe₂;Ar′: CHMe₂, C′HMe₂), 24.5, 23.9, 23.5, 23.4, 22.9, 22.9, 22.8, 22.2,21.71, 21.65, 20.9 (H₂C═CHMe; Ar: CHMeMe′, C′HMeMe′; Ar′: CHMeMe′,C′HMeMe′, N═C(Me)—C′(Me)═N), 16.9 (J_(CH)=137.5, PdMe), 15.0(O(CH₂CH₃)₂).

Example 201 {[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CHMe)}BAF⁻ and{[(2,6-i-PrPh)₂DABH₂]Pd(P)(H₂C═CHMe)}BAF⁻

[1132] This olefin complex, {[(2,6-i-PrPh)₂DABH₂]PdMe (H₂C═CHMe)}BAF⁻,was prepared following using both of the synthetic routes used inExample 197, using one equiv of propylene: ¹H NMR (CD₂Cl₂, 400 MHz, −80°C.) δ8.40 and 8.24 (s, 1 each, N═C(H)—C′(H)═N), 7.72 (s, 8, BAF: H_(o)),7.53 (s, 4, BAF: H_(p)), 7.40-7.27 (m, 6, H_(aryl)), 5.41 (br m,H₂C═CHMe), 4.39 (d, 1, J=8.09, HH′C═CHMe), 4.14 (br d, 1, J=15.29,HH′C═CHMe), 3.10 (br m, 1, CHMe₂), 2.87 (overlapping septets, 2, C′HMe₂,C″HMe₂), 2.59 (br septet, 1, C′″HMe₂), 1.64 (d, J=6.07, H₂C═CHMe), 1.39and 1.03 (d, 3 each, J=6.4, CHMeMe′), 1.27, 1.27, 1.14 and 1.1 (d, 3each, J=5.9-6.7, C′HMeMe′, C″HMeMe′), 1.23 and 1.1 (d, 3 each, J=6.8,C′″HMeMe′), 0.47 (PdMe); ¹³C NMR (CD₂Cl₂, 100 MHz, −80° C.) δ167.1(J_(CH)=181.6, N═C(H)), 163.0 (J_(CH)=182.1, N═C′(H)), 161.3 (q,J_(BC)=50.0, BAF: C_(ipso)), 140.5 and 140.0 (Ar, Ar′: C_(ipso)), 138.5,138.3, 137.7 and 137.2 (Ar: C_(o), C_(o)′; Ar′: C_(o), C_(o)′), 134.2(BAF: C_(o)), 128.9 and 128.8 (Ar, Ar′: C_(p)), 128.1 (q, J_(CF)=31.1,BAF: C_(m)), 124.0 (q, J_(CF)=272.5, BAF: CF₃), 124.6, 123.8, 123.8 and123.6 (Ar: C_(m), C_(m)′; Ar′: C_(m), C_(m)′), 117.1 (BAF: C_(p)), 116.4(J_(CH)=160.3, H₂C═CHMe), 85.4 (J_(CH)=159.9, H₂C═CHMe), 65.7(O(CH₂CH₃)₂), 29.2, 28.7, 28.5 and 28.0 (Ar: CHMe₂, C′HMe₂; Ar′: CHMe₂,C′HMe₂), 26.0, 24.4, 24.03, 23.97, 23.7, 21.9, 21.8, 21.7 and 21.6(H₂C═CHMe; Ar: CHMeMe′, C′HMeMe′; Ar′: CHMeMe′, C′HMeMe′), 16.6(J_(CH)=142.1, PdMe), 15.0 (O(CH₂CH₃)₂).

[1133] In the presence of 10 equiv of propylene, chain growth wasmonitored at −20° C., thus enabling{[(2,6-i-PrPh)₂DABH₂]Pd[(CHMeCH₂)Me](H₂C═CHMe)}BAF⁻, intermediates to beobserved (CD₂Cl₂, 400 MHz, −20° C.):{[(2,6-i-PrPh)₂DABMe₂]Pd((CHMeCH₂)_(n)Me)(H₂C═CHMe)}⁺BAF⁻ N═CHC′H═NHH′C═CHMe HH′C═CHMe C═CHMe (CHMeCH₂)_(n)Me n δ δ mult J δ mult J δ multδ mult J δ 0 8.40 8.26 d 14.4 4.25 d 8.6 4.47 m 5.45 s 0.59 1 8.38 8.24d 14.4 3.98 d 7.4 4.25 m 5.55 t 7.1 0.51 >1 8.39 8.23 d 13.7 4.07 d 8.04.41 m 5.42

Example 202

[1134] The compound {[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CHCH₂Me)}BAF⁻ was madeusing both the synthetic methods described in Example 197, except1-butene was used. ¹H NMR (CD₂Cl₂, 400 MHz, −75° C.) δ8.44 and 8.28 (s,1 each, N═C(H)—C′(H)═N), 7.74 (s, 8, BAF: C_(o)), 7.56 (s, 4, BAF:C_(p)), 7.5-7.2 (m, 6, H_(aryl)) 5.4 (m, 1, H₂C═CHCH₂CH₃), 4.36 (d, 1,J=8.2, HH′C═CHCH₂CH₃), 4.13 (br m, 1, HH′C═CHCH₂CH₃), 3.14, 2.92, 2.92and 2.62 (m, 1 each, Ar, Ar′: CHMe₂, C′HMe₂), 1.95 and 1.65 (m, 1 each,H₂C═CHCHH′CH₃), 1.5-1.0 (d, 3 each, Ar, Ar′: CHMeMe′, C′HMeMe′), 0.60(s, 3, PdMe).

[1135] Isomerization to cis- and trans-2-butene began at −78° C. and wasmonitored at −15° C. along with chain growth. For Pd[P] species,formation of the 1-butene complex occurred selectively in the presenceof cis- and trans-2-butene. Consumption of all olefins was observed at20° C.

Examples 203 {[(2,6-i-PrPh)₂DABH₂]PdMe(CH₃CH═CHCH₃)}BAF⁻

[1136] Experiments involving the reaction of the bispalladium(μ-Cl)compound/NaBAF (as in Example 197) with trans-2-butene and thebispalladium(μ-Cl) compound alone with cis-2-butene led to partialformation of the corresponding olefin complexes. An equilibrium wasobserved between the ether adduct and the olefin adduct when a compoundof the type {[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF⁻ was reacted with oneequiv of cis- or trans-2-butene. Addition of excess 2-butene led tocomplete formation of the olefin adduct. Chain growth, which wasmonitored at 0° C. to room temperature, led to complete consumption ofbutenes. Some butene isomerization occurred during the course of theoligomerization and small amounts of β-hydride elimination products(disubstituted internal olefins and trisubstituted olefins) wereobserved. Oligomer methylene and methyl groups were observed at 1.3 and0.8 ppm, respectively. Diagnostic ¹H NMR spectral data for the butenecomplexes follows:

[1137] {[(2,6-i-PrPh)₂DABH₂]PdMe(trans-CH₃CH═CHCH₃)}BAF⁻.

[1138]¹H NMR (CD₂Cl₂, 400 MHz, −39° C.) δ8.43 and 8.29 (s, 1 each,N═C(H)—C(H)═N), 5.27 and 4.72 (m, 1 each, CH₃CH═C′HCH₃), 0.73 (PdMe);¹³C NMR (CD₂Cl₂, 100 MHz, −95° C.) δ166.8 (J_(CH)=181.5, N═C(H)), 163.2(J_(CH)=179.8, N═C′(H)), 161.2 (q, J_(BC)=49.5, BAF: C_(ipso)) 141.3 and139.9 (Ar, Ar′: C_(ipso)), 138.4, 138.2, 138.0 and 137.0 (Ar, Ar′:C_(o), C_(o)′), 134.0 (BAF: C_(o)), 128.74 and 128.71 (Ar, Ar′: C_(p)),128.0 (q, J_(CF)=31.9, BAF: C_(m)), 125.4 (J_(CH)=150.0, freeMeCH═CHMe), 123.8 (q, J_(CF)=272.5, BAF: CF₃), 124.8, 123.7, 123.5 and123.4 (Ar, Ar′: C_(o), C_(o)′), 117.0 (BAF: C_(p)), 107.0 and 106.8(J_(CH)˜152, MeCH═C′HMe), 65.6 (free O(CH₂CH₃)₂), 29.5, 28.3, 27.6,26.5, 24.1, 23.8, 23.6, 21.5, 21.3, 21.2, 20.4, 19.9, 19.6,. 17.9, 17.5(Ar, Ar′: CHMeMe′, C′HMeMe′; MeCH═C′HMe), 17.7 (free MeCH═CHMe), 15.0(PdMe), 14.7 (O(CH₂CH₃)₂).

[1139] {[(2,6-i-PrPh)₂DABH₂]PdMe(cis-CH₃CH═CHCH₃)}BAF⁻. ¹H NMR (CD₂Cl₂,400 MHz, −75° C.) δ8.37 and 8.25 (s, 1 each, N═C(H)—C′(H)═N), 5.18 (q,2, CH₃CH═CHCH₃), 1.63 (d, 6, J=4.9, CH₃CH═CHCH₃), 0.47 (PdMe).

[1140] References for the synthesis of bis(oxazoline) ligands and theirtransition metal complexes: Corey, E. J.; Imai, N.; Zang, H. Y. J. Am.Chem. Soc. 1991, 113, 728-729. Pfaltz, A. Acc. Chem. Res. 1993, 26,339-345, and references within.

Example 204

[1141] 2,2-bis{2-[4(S)-methyl-1,3-oxazolinyl]}propane (500 mg, 2.38mmol) was dissolved in 10 mL CH₂Cl₂ in a Schlenk tube under a N₂atmosphere. This solution was added via cannula to a suspension of(1,2-dimethoxyethane)NiBr₂ (647 mg, 2.10 mmol) in 30 mL of CH₂Cl₂. Thesolution was stirred for 18 hours. The solvent was evaporated underreduced pressure. The product,2,2-bis{2-[4(S)-methyl-1,3-oxazolinyl]}propaneNi(Br₂), was washed with3×15 mL of hexane. The product was isolated as a purple powder (0.85 g,84% yield).

Example 205

[1142] The product of Example 204 (14.2 mg, 3.3×10⁻⁵ mol) and toluene(75 mL) were combined in a Schlenk flask under 1 atmosphere ethylenepressure. The solution was cooled to 0° C., and 3.0 mL of a 10% MAO (100eq) solution in toluene was added. The resulting yellow solution wasstirred for 40 hours. The oligomerization was quenched by the additionof H₂O and a small amount of 6 M HCl. The organic fraction was separatedfrom the aqueous fraction, and the toluene was removed under reducedpressure. A colorless oil resulted (0.95 g of oligomer). Thisillustrates that polymerization may be effected by such Pd, Ni and/or Cobisoxazoline complexes which are substituted in both 4 positions of theoxazoline ring by hydrocarbyl and substituted hydrocarbyl groups.

Example 206 [(COD)Pdme(NCMe)]⁺BAF⁻

[1143] To CODPdMeCl (110 mg, 0.37 mmol) was added a solution ofacetonitrile (0.08 mL, 1.6 mmol) in 25 mL CH₂Cl₂. To this colorlesssolution was added Na⁺BAF⁻ (370 mg, 0.4 mmol). A white solid immediatelyprecipitated. The mixture was stirred at −20° C. for 2 hours. Thesolution was concentrated and filtered. Removal of solvent under reducedpressure resulted in a glassy solid. ¹H NMR (CD₂Cl₂) δ5.78 (mult, 2H),δ5.42 (mult, 2H), δ2.65 (mult, 4H), δ2.51 (9 mult, 4H), δ2.37 (s, 3H,NCMe), δ1.19 (s, 3H, Pd-Me), δ7.72 (s, 8, BAF⁻, H_(o)), δ7.56 (s, 4,BAF⁻, H_(p)).

Example 207

[1144] [2,6-(i-Pr)₂PhDABH₂]NiBr₂ (10 mg, 1.7×10⁻⁵ mol), toluene (13 mL),and 1-hexene (38 mL) were combined in a Schlenk flask under an argonatmosphere. A 10% MAO solution (1.5 mL, 100 eq) in toluene was added toa suspension of the diimine nickel dihalide. The resulting purplesolution was stirred at room temperature for 1 hour. The polymerizationwas quenched and the polymer precipitated from acetone. The resultingcolorless polymer was dried in vacuo (2.5 g). GPC (toluene, polystyrenestandards) M_(n)=330,000; M_(w)=590,000; M_(n)/M_(w)=1.8.

Example 208

[1145] [(2,6-i-PrPh)₂DABH₂]NiBr₂ (10 mg, 1.7×10⁻⁵ mol) was added to asolution which contained toluene (30 mL) and 1-octene (20 mL). A 10%solution of MAO (1.5 mL, 100 eq) in toluene was added. The resultingpurple solution was allowed to stir for 4 hours at room temperature.Solution viscosity increased over the duration of the polymerization.The polymer was precipitated from acetone and dried in vacuo resultingin 5.3 g of copolymer. M_(n)=15,200; M_(w)=29,100; M_(w)/M_(n)=1.92.

Example 209

[1146] [(2,6-i-PrPh)₂DABMe₂]Ni(CH₃)₂ (20 mg, 4.1×10⁻⁵ mol) and MAO (35.7mg, 15 eq) were combined as solids in an NMR tube. The solid mixture wascooled to −78° C. and dissolved in 700 μL of CD₂Cl₂. While cold, 10 μLof ether d¹⁰ was added to stabilize the incipient cation.

[1147]¹H NMR spectrum were recorded at 253, 273, and 293° K. It wasapparent that the starting nickel dimethyl complex was disappearing anda new nickel complex(es) was being formed. Activation of the dimethylcomplex was occurring through methane loss (s,δ 0.22). After 2 hours at293° K. all of the starting species had disappeared. To test forethylene polymerization activity, 5000 μL (10 eq) of ethylene was addedvia gas tight syringe to the solution at −78° C. The consumption ofethylene was monitored by ¹H NMR spectroscopy. The onset of ethyleneuptake was observed at 223° K. and all of the ethylene was consumed uponwarming the probe to 293° K. The persistence of the Ni-Me signal duringthe experiment suggests that under these conditions propagation isfaster than initiation. Solid polyethylene was observed upon removingthe NMR tube from the probe.

Example 210

[1148] [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (50 mL) and 1-hexene (25 mL) under a N₂ atmosphere. Et₂AlCl(0.01 mL, 10 eq) was added to the polymerization mixture. The resultingpurple solution was allowed to stir for 4 hours. After 4 hours thepolymerization was quenched and the polymer precipitated from acetone.The polymerization yielded 2.05 g poly(1-hexene)(731 TO). (GPC, toluene,polystyrene standards) M_(n)=305,000; M_(w)=629,000; M_(w)/M_(n)=2.05.T_(g)=−57° C., T_(m)=52° C. T_(m)=−57° C., T_(g)=−20° C. ¹H NMR (C₆D₅Cl,142° C.) 10 methyls per 100 carbons. This number is significantly lessthan would be expected for strictly atactic 1-hexene.

Example 211

[1149] Concentration dependence on catalyst activity in nickel catalyzedpolymerization of α-olefins. A series of homopolymerizations of 1-hexenewere run at 10%, 15%, 20%, 30%, 40%, and 75% 1-hexene by volume. In eachof the above cases 10 mg of [(2,6-i-PrPh)₂DABH₂]NiBr₂ was taken up intoluene and 1-hexene (50 mL total volume 1-hexene+toluene). All of thepolymerizations were run at 250° C. and activated by the addition of 1.5mL of a 10% MAO solution in toluene. The polymerizations were stirredfor 1 hour and quenched upon the addition of acetone. The polymer wasprecipitated from acetone and dried in vacuo. 10% by volume 1-hexeneyielded 2.5 g poly(1-hexene), 15% by volume 1-hexene yielded 2.6 gpoly(1-hexene), 20% by volume 1-hexene yielded 3.0 g poly(1-hexene), 30%by volume 1-hexene yielded 2.6 g poly(1-hexene), 40% by volume 1-hexeneyielded 2.6 g poly(1-hexene), 75% by volume 1-hexene yielded 2.5 gpoly(1-hexene).

Example 212

[1150] FeCl₂ (200 mg, 1.6 mmol) and 20 ml of CH₂Cl₂ were combined in aSchlenk flask under an argon atmosphere. In a separate flask, 550 mg(2,6-i-PrPh)₂DABMe₂ and 20 ml CH₂Cl₂ were combined, resulting in ayellow solution. The ligand solution was slowly (2 hr) transferred viacannula into the suspension of FeCl₂. The resulting solution was stirredat 25° C. After 4 hr. the solution was separated from the unreactedFeCl₂ by filter cannula (some purple solid was also left behind). Thesolvent was removed in vacuo to give a purple solid (0.53 g, 71% yield).A portion of the purple solid was combined with 50 ml of toluene under 1atm of ethylene. The solution was cooled to 0° C., and 6 ml of a 10% MAOsolution in toluene was added. The mixture was warmed to 25° C. andstirred for 18 hr. The polymer was precipitated by acetone, collected bysuction filtration, and washed with 6M HCl, water and acetone. The whitepolymer was dried under reduced pressure. Yield 13 mg.

Example 213

[1151] A 58-mg (0.039-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}BAF⁻ was placed in a 600-mLstirred autoclave under nitrogen with 150 mL of deaerated water. Thismixture was pressurized to 5.5 MPa with ethylene and was stirred at 23°C. for 68 hr. When the ethylene was vented, the autoclave was found tobe full of rubbery polymer: on top was a layer of white, fluffyelastomeric polyethylene, while beneath was gray, dense elastomericpolyethylene. The water was poured out of the autoclave; it was a hazylight blue, containing a tiny amount of emulsified polyethylene;evaporation of the whole aqueous sample yielded a few mg of material.The product was dried under high vacuum to yield 85.5 g of amorphouselastomeric polyethylene, which exhibited a glass transition temperatureof −61° C. and a melting endotherm of −31° C. (16 J/g) by differentialscanning calorimetry. H-1 NMR analysis (CDCl₃): 105 methyl carbons per1000 methylene carbons. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=42,500; M_(w)=529,000;M_(w)/M_(n)=12.4. This example demonstrates the use of pure water as apolymerization medium.

Example 214

[1152] A 73-mg (0.049 mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}BAF⁻ was placed in a 600-mLstirred autoclave under nitrogen with 150 mL of deaerated water; to thiswas added 3.1 mL (3.3 g) of Triton® X-100 nonionic surfactant. Thismixture was pressurized to 5.8 MPa with ethylene and was stirred at 23°C. for 17 hr. When the ethylene was vented, most of the emulsion cameout the valve due to foaming; it was caught in a flask. There waspolymer suspended in the emulsion; this was filtered to give, after MeOHand acetone washing and air-drying, 2.9 g of amorphous polyethylene as afine, gray rubber powder. The filtrate from the suspended polymer was aclear gray solution; this was concentrated on a hot plate to yieldrecovered Triton® X-100 and palladium black. There was no polymer in theaqueous phase. The elastomeric polyethylene product exhibited a glasstransition temperature of −50° C. and a melting endotherm of 48° C. (5J/g) by differential scanning calorimetry. H-1 NMR analysis (CDCl₃): 90methyl carbons per 1000 methylene carbons. Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=31,000;M_(w)=311,000; M_(w)/M_(n)=10.0. This example demonstrates the aqueousemulsion polymerization of ethylene in the presence of a non-ionicsurfactant.

Example 215

[1153] A 93-mg (0.110-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ was placed in a 600-mLstirred autoclave under nitrogen with 150 mL of deaerated water; to thiswas added 0.75 g (1.4 mmol) of FC-95® anionic fluorosurfactant(potassium perfluorooctansulfonate). This mixture was pressurized to 5.1MPa with ethylene and was stirred at 23° C. for 15 hr. The ethylene wasvented; the product consisted of polymer suspended in emulsion as wellas some polymer granules on the wall of the autoclave; the emulsion wasfiltered to give, after MeOH and acetone washing and air-drying, 2.4 gof amorphous polyethylene as a fine, gray rubber powder. The hazyblue-gray aqueous filtrate was evaporated to yield 0.76 g of residue;hot water washing removed the surfactant to leave 0.43 g of dark brownsticky polyethylene rubber. H-1 NMR (CDCl₃) analysis: 98 CH₃'s per 1000CH₂'s. Differential scanning calorimetry: melting point: 117° C. (111J/g); glass transition: −31° C. (second heat; no apparent Tg on firstheat). This example demonstrates the aqueous emulsion polymerization ofethylene in the presence of a anionic surfactant. This example alsodemonstrates that a true aqueous emulsion of polyethylene can beobtained by emulsion polymerization of ethylene with these catalysts inthe presence of an appropriate surfactant.

Example 216

[1154] A 90-mg (0.106-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ was placed in a 600-mLstirred autoclave under nitrogen with 150 mL of deaerated water; to thiswas added 0.75 g (2.1 mmol) of cetyltrimethylammonium bromide cationicsurfactant. This mixture was pressurized to 5.2 MPa with ethylene andwas stirred for 66 hr at 23° C. The ethylene was vented; the productconsisted of polymer suspended in a dark solution; this was filtered togive, after MeOH and acetone washing and air-drying, 0.13 g of amorphouspolyethylene as a tacky, gray rubber powder. There was no polymer in theaqueous phase. H-1 NMR (CDCl₃) analysis: 96 CH₃'s per 1000 CH₂'s.Differential scanning calorimetry: glass transition: −58° C.; meltingendotherms: 40°, 86°, 120° C. (total: 20 J/g). This example demonstratesthe aqueous emulsion polymerization of ethylene in the presence of acationic surfactant.

Example 217

[1155] An 87-mg (0.103-mmol) sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ was placed in a 600-mLstirred autoclave under nitrogen. To this was added 100 mL of dry,deaerated methyl acrylate containing 100 ppm of phenothiazine as afree-radical polymerization inhibitor. The autoclave was stirred andpressurized to 300 psig with ethylene over 5 min. The autoclave was thenpressurized to 600 psig with an additional 300 psig of carbon monoxide(300 psig E+300 psig CO=600 psig). The reaction was stirred for 20 hr at23° C. as the autoclave pressure dropped to 270 psig. The ethylene wasthen vented; the autoclave contained a yellow solution which wasconcentrated by rotary evaporation, taken up in methylene chloride,filtered, and again concentrated to yield 0.18 g of dark brown viscousoil. The product was washed with hot acetone to remove the browncatalyst residues and was held under high vacuum to yield 55 mg of acolorless, viscous liquid terpolymer. The infrared spectrum exhibitedcarbonyl absorbances at 1743 (ester), 1712 (ketone), and 1691 cm⁻¹. H-1NMR (CDCl₃) analysis: 76CH₃'s per 1000 CH₂; there were peaks at 2.3 (t,CH ₂COOR), 2.7 (m, CH ₂CO), and 3.66 ppm (COOCH ₃). The polymercontained 3.3 mol % MA (9.4 wt % MA). The carbon monoxide content wasnot quantified, but the absorbance in the infrared spectrum of thepolymer due to ketone was about ½ to ⅔ the absorbance due to acrylateester. This example demonstrates the use of carbon monoxide as amonomer.

Example 218

[1156] A 20-mg (0.035-mmol) sample of NiBr₂[2-NpCH═N(CH₂)₃N═CH-2-Np],where Np=naphthyl, (see structure below) was magnetically stirred undernitrogen in a 50-mL Schlenk flask with 25 mL of dry deaerated, toluene.Then 0.6 mL of polymethylalumoxane (3.3M) was injected; the light pinksuspension became a dark gray-green solution, eventually with blackprecipitate. The mixture was immediately pressurized with ethylene to 7psig and was stirred at 23° C. for 18 hr, during which time the mixturebecame a clear yellow solution with black, sticky precipitate. Theethylene was vented; the offgas contained about 3% butenes (90:101-butene: trans-2-butene) by gas chromatography (30-m Quadrex GSQ®Megabore column; 50-250° C. at 10°/min). The toluene solution wasstirred with 6N HCl and methanol and was separated; concentration of thetoluene solution followed by acetone rinsing the residue yielded 85 mgof liquid polyethylene. H-1 NMR (CDCl₃) analysis: 209 CH₃'s per 1000CH₂'s. This example demonstrates the efficacy of a catalyst with abis-imine ligand in which the imine groups are not alpha to one another.

Example 219

[1157] A 17-mg (0.027-mmol) sample of [(2,6-i-PrPh)₂DABMe₂]ZrCl₄ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the yellow suspension became an orange-yellow solution. Themixture was pressurized with ethylene to 7 psig and was stirred at 23°C. for 20 hr, during which time polymer slowly accumulated on the stirbar and eventually rendered the solution unstirrable. The toluenesolution was stirred with 6N HCl and methanol and was filtered to yield(after MeOH and acetone washing and air-drying) 1.01 g of white, fluffypolyethylene. Differential scanning calorimetry exhibited a meltingpoint of 131° C. (124 J/g). This example demonstrates the efficacy of aZr(IV) catalyst bearing a diimine ligand.

Example 220

[1158] A 14-mg (0.024-mmol) sample of [(2,6-i-PrPh)₂DABMe₂]TiCl₄ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deareated toluene (distilled from Na under N₂). Then 0.6 mL ofpolymethylalumoxane (3.3M) was injected; the yellow suspension became adark brown suspension with some precipitate. The mixture was pressurizedwith ethylene to 7 psig and was stirred at 23° C. for 3 hr, during whichtime polymer accumulated and rendered the solution unstirrable. Thetoluene solution was stirred with 6N HCl and methanol and was filteredto yield, after MeOH and acetone washing and air-drying, 1.09 g ofwhite, fluffy polyethylene. Differential scanning calorimetry exhibiteda melting point of 131° C. (161 J/g). This example demonstrates theefficacy of a Ti(IV) catalyst bearing a diimine ligand.

Example 221

[1159] A 28-mg (0.046-mmol) sample of [(2,6-i-PrPh)₂DABMe₂]CoBr₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.5 mL of polymethylalumoxane (3.3M) wasinjected, resulting in a deep purple solution, and the mixture waspressurized immediately with ethylene to 7 psig and stirred at 23° C.for 17 hr. The solution remained deep purple but developed someviscosity due to polymer. The ethylene was vented; the offgas contained1.5%

[1160] 1-butene by gas chromatography (30-m Quadrex GSQ® Megaborecolumn; 50-250° C. at 10°/min). The toluene solution was stirred with 6NHCl/methanol and was separated; concentration of the toluene solutionyielded, after drying under high vacuum, 0.18 g of elastomericpolyethylene. A film of polymer cast from chlorobenzene was stretchywith good elastic recovery. Differential scanning calorimetry: glasstransition: 41° C.; melting endotherm: 43° C. (15 J/g). This exampledemonstrates the efficacy of a cobalt (II) catalyst bearing a diimineligand.

Example 222

[1161] A 35-mg (0.066-mmol) sample of [(2,6-i-PrPh)₂DABMe₂]FeCl₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the deep purple-blue solution became a royal purple solution,which evolved to deep green-black over time. The mixture was immediatelypressurized with ethylene to 7 psig and was stirred at 23° C. for 70 hr,during which time the mixture became a pale green solution with black,sticky precipitate. The ethylene was vented; the toluene solution wasstirred with 6N HCl and methanol and was filtered to yield 90 mg ofpolyethylene.

[1162] Differential scanning calorimetry: melting endotherm: 128° C. (84J/g). This example demonstrates the efficacy of a iron (II) catalystbearing a diimine ligand.

Example 223

[1163] A mixture of 3.2 g of the polyethylene product of Example 96, 60mg (1.9 wt %) of dicumyl peroxide, and 50 g (1.6 wt %) oftriallylisocyanurate (TAIC) was dissolved in 100 mL of THF. The polymerwas precipitated by stirring the solution in a blender with water; theperoxide and TAIC are presumed to have stayed in the polymer. Thepolymer was pressed into a clear, rubbery, stretchy film at 125° C.Strips of this film were subsequently pressed at various temperatures(100° C., 150° C., 175° C., 200° C.) for various times (1 min, 5 min, 10min) to effect peroxide-induced free-radical crosslinking. The curedsheets were all clear and stretchy and shorter-breaking: 100° C. for 10min gave no apparent cure, while 150° C./5 min seemed optimal. The curedfilms came closer to recovering their original dimensions than theuncured films. This example demonstrates peroxide curing of theamorphous elastomeric polyethylene.

Example 224

[1164] A 28-mg (0.050-mmol) sample of TiCl₄[2-NpCH═N(CH₂)₂N═CH-2-Np],where Np=naphthyl, (see structure below) was magnetically stirred undernitrogen in a 50-mL Schlenk flask with 25 mL of dry, deaerated toluene.Then 0.6 mL of polymethylalumoxane (3.3M) was injected; the orangesuspension became reddish-brown. The mixture was immediately pressurizedwith ethylene to 7 psig and was stirred at 23° C. for 66 hr. The toluenesolution was stirred with 6N HCl and methanol and was filtered to yield,after methanol washing and air-drying, 1.30 g of white, fluffypolyethylene.

[1165] Differential scanning calorimetry: melting endotherm: 135° C.(242 J/g).

[1166] This example demonstrates the efficacy of a catalyst with abis-imine ligand in which the imine groups are not alpha to one another.

Example 225

[1167] A 33-mg (0.053-mmol) sample of [(2,6-i-PrPh)₂DABMe₂]ScCl₃-THF wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the pale orange solution became bright yellow. The mixture wasimmediately pressurized with ethylene to 7 psig and was stirred at 23°C. for 17 hr, during which time the mixture remained yellow and granularsuspended polymer appeared. The ethylene was vented; the toluenesolution was stirred with 6N HCl and methanol and was filtered to yield2.77 g of white, granular polyethylene. This example demonstrates theefficacy of a scandium (III) catalyst bearing a diimine ligand.

Example 226 (2-t-BuPh)2DABAN

[1168] This compound was made by a procedure similar to that of Example25. Three mL (19.2 mmol) of 2-t-butylaniline and 1.71 g (9.39 mmol) ofacenaphthenequinone were partially dissolved in 50 mL of methanol(acenaphthenequinone was not completely soluble). An orange product wascrystallized from CH2Cl2 (3.51 g, 84.1%). 1H NMR (CDCl3, 250 MHz) d 7.85(d, 2H, J=8.0 Hz, BIAN: Hp), 7.52 (m, 2H, Ar: Hm), 7.35 (dd, 2H, J=8.0,7.3 Hz, BIAN: Hm), 7.21 (m, 4H, Ar: Hm and Hp), 6.92 (m, 2H, Ar: Ho),6.81 (d, 2H, J=6.9 Hz, BIAN: Ho), 1.38 (s, 18H, C(CH3)3).

Example 227

[1169] Methyl vinyl ketone was stirred over anhydrous K₂CO₃ and vacuumtransferred on a high vacuum line to a dry flask containingphenothiazine (50 ppm). Ethylene and methyl vinyl ketone (5 ml) werecopolymerized according to Example 16 using catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.084 g, 0.10 mmol)to give 0.46 g copolymer (0.38 g after correcting for catalyst residue).¹H-NMR (CDCl₃): 0.75-0.95(m, CH₃); 0.95-1.45(m, CH and CH₂); 1.55(m, —CH₂CH₂C(O)CH₃); 2.15(s, —CH₂CH₂C(O)CH ₃); 2.4(t, —CH₂CH ₂C(O)CH₃). Basedon the triplet at 2.15, it appears that much of the ketone functionalityis located on the ends of hydrocarbon branches. Integration shows thatthe copolymer contains 2.1 mole % methyl vinyl ketone, and 94 methylcarbons (exclusive of methyl ketones) per 1000 methylene carbons. Theturnover numbers are 128 equivalents of ethylene and 3 equivalents ofmethyl vinyl ketone per Pd. GPC (THF, PMMA standard): Mn=5360 Mw=7470Mw/Mn=1.39.

Example 228

[1170] A Schlenk flask containing 122 mg (0.0946 mmol) of{[(4-MePh)₂DABMe₂]PdMe(N###CMe)}⁺BAF⁻ was placed under a CO atmosphere.The yellow powder turned orange upon addition of CO, and subsequentaddition of 20 mL of CH₂Cl₂ resulted in the formation of a clear redsolution. t-Butylstyrene (10 mL) was added next and the resulting orangesolution was stirred for 25.7 h at room temperature. The solution wasthen added to methanol in order to precipitate the polymer, which wascollected by filtration and dried in a vacuum oven at 50° C. overnight(yield=4.03 g): GPC Analysis (THF, polystyrene standards): M_(w)=8,212;M_(n)=4,603; PDI=1.78. The ¹H NMR spectrum (CDCl₃, 400 MHz) of theisolated polymer was consistent with a mixture of copolymer andpoly(t-butylstyrene).

[1171] Mixtures of alternating copolymer and poly(t-butylstyrene) wereobtained from this and the following polymerizations and were separatedby extraction of the homopolymer with petroleum ether. When R² and R⁵were 4-MePh (this example) atactic alternating copolymer was isolated.When R² and R⁵ were 2,6-i-PrPh (Example 229) predominantly syndiotacticalternating copolymer was isolated. (Spectroscopic data for atactic,syndiotactic, and isotactic t-butylstyrene/CO alternating copolymers hasbeen reported: M. Brookhart, et al., J. Am. Chem. Soc. 1992, 114,5894-5895; M. Brookhart, et al., J. Am. Chem. Soc. 1994, 116,3641-3642.)

[1172] Petroleum ether (˜200 mL) was added to the polymer mixture inorder to extract the homopolymer, and the resulting suspension wasstirred vigorously for several h. The suspension was allowed to settle,and the petroleum ether solution was decanted off of the gray powder.The powder was dissolved in CH₂Cl₂ and the resulting solution wasfiltered through Celite. The CH₂Cl₂ was then removed and the light graypowder (0.61 g) was dried in vacuo. ¹H and ¹³C NMR spectroscopic dataare consistent with the isolation of atactic alternating copolymer: ¹HNMR (CDCl₃, 300 MHz) δ7.6-6.2 (br envelope, 4, H_(aryl)), 4.05 and 3.91(br, 1, CHAr′), 3.12 and 2.62 (br, 2, CH₂), 1.26-1.22 (br envelope, 9,CMe₃); ¹³C NMR (CDCl₃, 75 MHz) δ207.5-206.0 (br envelope, —C(O)—),150.0-149.0 (br, Ar′: C_(p)), 135.0-133.8 (br envelope, Ar′: C_(ipso)),127.9 (Ar′: C_(m)), 126.0-125.0 (br, Ar′: C_(o)), 53.0-51.0 (brenvelope, CHAr′), 46.0-42.0 (br envelope, CH₂), 34.3 (CMe₃), 31.3(CMe₃).

Example 229

[1173] The procedure of Example 228 was followed using 134 mg (0.102mmol) {[(2,6-i-PrPh)₂DABMe₂]PdMe(N###CMe)}⁺BAF⁻. A mixture (2.47 g) ofcopolymer and poly(t-butylstyrene) was isolated. GPC Analysis (THF,polystyrene standards): M_(w)=10,135; M_(n)=4,922; PDI=2.06. Followingthe extraction of the homopolymer with petroleum ether, 0.49 g ofoff-white powder was isolated. ¹H and ¹³C NMR spectroscopic data areconsistent with the isolation of predominantly syndiotactic copolymer,although minor resonances are present: ¹H NMR (CDCl₃, 300 MHz) δ7.20 (d,2, J=8.14, Ar′: H_(o) or H_(m)) 6.87 (d, 2, J=7.94, Ar′: H_(o) orH_(m)), 3.91 (dd, 1, J=9.06, 3.16, CHAr′), 3.15 (dd, 1, J=18.02, 9.96,CHH′), 2.65 (dd, 1, J=17.90, CHH′), 1.25 (S, 9, CMe₃); ¹³C NMR (CDCl₃,75 MHz) δ207.0 (—C(O)—), 149.8 (Ar′: C_(p)), 134.5 (Ar′: C_(ipso)),127.8 (Ar′: C_(m)), 125.6 (Ar′: C_(o)), 51.7 (CHAr′), 45.6 (CH₂), 34.3(CMe₃), 31.3 (CMe₃).

Example 230

[1174] A Schlenk flask containing 74.3 mg (0.0508 mmol) of{[(2,6-i-PrPh)₂DABMe₂]PdMe(OEt₂)}⁺BAF⁻ was evacuated, cooled to −78° C.and then placed under an atmosphere of ethylene/CO (1:1 mixture).Following the addition of 50 mL of chlorobenzene, the reaction mixturewas allowed to warm to room temperature and stirred. A small amount ofwhite precipitate appeared on the sides of the flask after 0.5 h andmore precipitate formed during the next two days. After stirring for47.2 h, the reaction mixture was added to methanol and the resultingsuspension was stirred. The precipitate was then allowed to settle, andthe methanol was decanted, leaving behind a cream powder (0.68 g), whichwas dried in a vacuum oven at 70° C. for one day. ¹H and ¹³C NMRspectroscopic data are consistent with the isolation of an alternatingcopolymer of ethylene and carbon monoxide: ¹H NMR(CDCl₃/pentafluorophenol, 400 MHz) δ2.89 (—C(O)—CH₂CH₂—C(O)—); ¹³C NMR(CDCl₃/pentafluorophenol, 100 MHz) δ212.1 (—C(O)—), 35.94 (CH₂).

[1175] For comparisons of the spectroscopic data of alternating E/COcopolymers herein with literature values, see for example: E. Drent, etal., J. Organomet. Chem. 1991, 417, 235-251.

Example 231

[1176] A Schlenk flask containing 73.2 mg (0.0500 mmol) of{[(2,6-i-PrPh)₂DABMe₂]PdMe(OEt₂)}⁺BAF⁻ was evacuated, cooled to −78° C.,and then back-filled with ethylene (1 atm). Chlorobenzene (50 mL) wasadded via syringe and the solution was allowed to warm to roomtemperature. After 0.5 h, the reaction vessel was very warm and ethylenewas being rapidly consumed. The reaction flask was then placed in aroom-temperature water bath and stirring was continued for a total of 3h. A very viscous solution formed. The atmosphere was then switched toethylene/carbon monoxide (1:1 mixture, 1 atm) and the reaction mixturewas stirred for 47.7 more hours. During this time, the solution becameslightly more viscous. The polymer was then precipitated by adding thechlorobenzene solution to methanol. The methanol was decanted off of thepolymer, which was then partially dissolved in a mixture of Et₂O, CH₂Cl₂and THF. The insoluble polymer fraction (2.71 g) was collected on asintered glass frit, washed with chloroform, and then dried in a vacuumoven at 70° C. for 12 h. The NMR spectroscopic data of the gray rubberymaterial are consistent with the formation of a diblock of branchedpolyethylene and linear poly(ethylene-carbon monoxide): ¹H NMR(CDCl₃/pentafluorophenol, 400 MHz) δ2.85 (—C(O)CH₂CH₂C(O)—), 2.77(—C(O)CH₂, minor), 1.24 (CH₂), 0.83 (CH₃); Polyethylene Block Branching:˜103 CH₃ per 1000 CH₂; Relative BlockLength[(CH₂CH₂)_(n)—(C(O)CH₂CH₂)_(m)]: n/m=2.0. ¹³C NMR(CDCl₃/pentafluorophenol, 100 MHz; data for ethylene-CO, block) δ211.6(—C(O)—), 211.5 (—C(O)—, minor), 35.9 (C(O)—CH₂CH₂—C(O)), 35.8 (C(O)CH₂,minor).

Example 232

[1177] A Schlenk flask containing 75.7 mg (0.0527 mmol) of{[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}⁺BAF⁻ was evacuated, cooled to −78° C.,and then back-filled with ethylene (1 atm). Chlorobenzene (50 mL) wasadded via syringe, the solution was allowed to warm to room temperatureand stirred for 3 h. The solution did not become warm or viscous duringthis time. The atmosphere was changed to ethylene/carbon monoxide (1:1mixture, 1 atm) and the solution was stirred for 47.7 more hours. Duringthis time, the reaction mixture became quite viscous and solvent-swollenpolymer precipitated on the sides of the flask. The polymer wasprecipitated by addition of the reaction mixture to methanol. Themethanol was decanted off of the rubbery polymer (4.17 g), which wasthen dried in a vacuum oven for one day at 70° C. Chloroform was thenadded to the polymer and the rubbery insoluble fraction (0.80 g) wascollected on a sintered glass frit. A ¹H NMR spectrum (CDCl₃, 400 MHz)of the chloroform-soluble polymer showed no carbon monoxideincorporation; only branched polyethylene was observed. NMRspectroscopic data for the chloroform-insoluble fraction was consistentwith the formation of a diblock of branched polyethylene and linearpoly(ethylene-carbon monoxide): ¹H NMR (CDCl₃/pentafluorophenol, 400MHz) δ2.88 (C(O)CH₂CH₂C(O)), 1.23 (CH₂), 0.83 (CH₃); Polyethylene BlockBranching: 132 CH₃ per 1000 CH₂; Relative BlockLength[(CH₂CH₂)_(n)—(C(O)CH₂CH₂)_(m)]: n/m=0.30; ¹³C NMR(CD₂Cl₂/pentafluorophenol, 100 MHz; data for ethylene-CO block) δ211.3(—C(O)—), 211.3 (—C(O)—, minor), 36.5 (—C(O)CH₂CH₂C(O)—), 36.4 (C(O)CH₂,minor).

Example 233

[1178] A 34-mg (0.053-mmol) sample of the crude product of Example 235,was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 25mL of dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M)was injected; the purple-pink suspension became a gold-green solutionwith black precipitate. The mixture was pressurized with ethylene to 152kPa (absolute) and was stirred for 20 hr. Within the first hour, polymerwas observed to be accumulating on the stir bar and the walls of theflask. The ethylene was vented and the toluene solution was stirred with6N HCl and methanol and was filtered to yield (after MeOH and acetonewashing and air-drying) 1.37 g of white, granular polyethylene. Thisexample demonstrates the efficacy of a catalyst with a 1,3-diimineligand.

Example 234 Synthesis of MeC(═N-2,6-C₆H₃-iPr₂)CH═C(NH-2,6-C₆H₃-iPr₂)Me

[1179] Concentrated HCl (0.3 ml, 3.6 mmol) was added to a solution of2,4-pentanedione (1.2 g, 12 mmol) and 2,6-diisopropylaniline (5.0 ml,26.6 mmol) in 15 ml ethanol. The reaction mixture was refluxed for 21 hduring which time a white solid precipitated. This was separated byfiltration, dried under vacuum and treated with saturated aqueous sodiumbicarbonate. The product was extracted with methylene chloride, and theorganic layer dried over anhydrous sodium sulfate. Removal of thesolvent afforded 1.43 g (28%) of the title compound as a whitecrystalline product; mp: 140-142° C.; ¹H NMR: (CDCl₃) δ12.12 (bs,1H,NH), 7.12 ( m, 6 H, aromatic), 4.84 (s, 1H, C═CH—C), 3.10 (m, 4H,isopropyl CH, J=7 Hz), 1.72 (s, 6H, CH₃), 1.22 (d, 12H, isopropyl CH₃,J=7 Hz), 1.12 (d, 12H, isopropyl CH₃, J=7 Hz). ¹³C NMR: (CDCl₃) δ161.36(C═N), 142.63 (aromatic C-1), 140.89 (aromatic C-2), 125.27 (aromaticC-4), 123.21 (aromatic C-3), 93.41 (—CH═), 28.43 (isopropyl CH), 24.49(isopropyl CH₃), 23.44 (isopropyl CH₃), 21.02 (CH₃). MS: m/z=418.333(calc. 418.335).

Example 235 Synthesis of an ethylene polymerization catalyst fromNi(MeOCH₂CH₂OMe)Br₂ and MeC(═N-2,6-C₆H₃-iPr₂)CH═C(NH-2,6-C₆H₃-iPr₂)

[1180] Ni(MeOCH₂CH₂OMe)Br₂ (0.110 g, 0.356 mmol) andMeC(═N-2,6-C₆H₃-iPr₂)CH═C(NH—C₆H₃-iPr₂)Me (0.150 g, 0.359 mmol) werecombined in 10 mL of methylene chloride to give a peach-coloredsuspension. The reaction mixture was stirred at room temperatureovernight, during which time a lavender-colored powder precipitated.This was isolated by filtration, washed with petroleum ether and driedaffording 0.173 g of material. This compound was used as the catalyst inExample 233.

Example 236 {[(2,6-i-PrPh)₂DABMe₂]Pd(MeCN)₂}(BF₄)₂

[1181] [Pd(MeCN)₄](BF₄)₂ (0.423 g, 0.952 mmol) and (2,6-i-PrPh)₂DABMe₂(0.385 g, 0.951 mmol) were dissolved in 30 mL acetonitrile undernitrogen to give an orange solution. The reaction mixture was stirred atroom temperature overnight; it was then concentrated in vacuo to afforda yellow powder. Recrystallization from methylene chloride/petroleumether at −40° C. afforded 0.63 g of the title compound as a yellowcrystalline solid. 1H NMR (CD₂Cl₂) δ7.51 (t, 2H, H_(para)), 7.34 (d, 4H,H_(meta)), 3.22 (sept, 4H, CHMe₂), 2.52 (s, 6H, N═CMe), 1.95 (s, 6H,NC≡Me), 1.49 (d, 12H, CHMe₂), 1.31 (d, 12H, CHMe₂).

Example 237 Ethylene Polymerization Catalyzed by{[(2,6-i-PrPh)₂DABMe₂]Pd(MeCN)₂}(BF₄)₂

[1182] A 100 mL autoclave was charged with a solution of{[(2,6-i-PrPh)₂DABMe₂]Pd(MeCN)₂}(BF₄)₂ (0.043 g, 0.056 mmol) dissolvedin 50 mL chloroform and ethylene (2.8 MPa). The reaction mixture wasstirred under 2.8 MPa ethylene for 9 h 15 min. During this time, thetemperature inside the reactor increased from 23 to 27° C. The ethylenepressure was then vented and volatiles removed from the reaction mixtureto afford 1.65 g of a viscous yellow oil. This was shown by ¹H NMR to bebranched polyethylene containing 94 methyl-ended branches per 1000methylenes.

Example 238 Ethylene polymerization byNi(COD)₂/(2,6-i-PrPh)₂DABMe₂∘HBAF(Et₂O)₂

[1183] Ni(COD)₂ (0.017 g, 0.06 mmol) and (2,6-i-PrPh)₂DABMe₂∘HBAF(Et₂O)₂(0.085 g, 0.06 mmol) were dissolved in 5 mL of benzene under nitrogen atroom temperature. The resulting solution was quickly frozen, and thenallowed to thaw under 6.9 MPa of ethylene at 50° C. The reaction mixturewas agitated under these conditions for 18 h affording a solvent swelledpolymer. Drying afforded 5.8 g of a polyethylene as a tough, rubberymaterial.

Example 239 Ethylene polymerization by Pd₂(dba)₃(dba=dibenzylideneacetone)/(2,6-i-PrPh)₂DABMe₂∘HBAF(Et₂O)₂

[1184] A sample of (Et₂O)⁻HBAF (200 mg, 0.20 mmol) was dissolved in 10mL of Et₂O. To this solution was added 1 equivalent of DABMe₂ (or otherα-diimine). The solution became red. Removal of the volatiles in vacuogave a red solid of the acid-α-diimine complex.

[1185] Pd₂(dba)₃ (0.054 g, 0.06 mmol) and(2,6-i-PrPh)₂DABMe₂∘HBAF(Et₂O)₂ (0.076 g, 0.05 mmol) were dissolved in 5mL of benzene under nitrogen at room temperature. The resulting solutionwas agitated under 6.9 MPa of ethylene at 50° C. for 18 h. The productmixture was concentrated to dryness in vacuo, affording an extremelyviscous oil. ¹H NMR showed the product to be branched polyethylenecontaining 105 methyl ended branches per 1000 methylenes.

Example 240

[1186] Toluene (30 mL), 4-vinylcyclohexene (15 mL), and 20 mg of[(2,6-i-PrPh)₂DABH₂]NiBr₂ (0.03 mmol) were combined in a Schlenk flaskunder an atmosphere of ethylene. A 10% MAO solution (3 mL) in toluenewas added. The resulting purple solution was stirred for 16 h. Afteronly a few hours, polymer began to precipitate and adhere to the wallsof the flask. The polymerization was quenched and the polymerprecipitated from acetone. The polymer was dried in vacuo overnightresulting in 100 mg of a white solid. Characterization by proton NMRsuggests in corporation of 4-vinylcyclohexene as a comonomer. ¹H NMR(CDCl₃) δ5.64 (m, vinyl, cyclohexene), 2.0-0.9 (overlapping m includingcyclohexyl methylene, methylene (PE), methine), 0.78 (methyl, PE). Thereare also some minor signals in the base line that suggests incorporationof the internal olefin (cyclohexene) and free α-olefin (4-vinyl).

Example 241

[1187] The catalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}SbF₆ ⁻(1.703 g, 2 mmol) was added to a 1 gal Hastalloy® autoclave. Theautoclave was sealed, flushed with nitrogen and then charged with 1500 gof SO₂. An over pressure of 3.5 MPa of ethylene was maintained for 24 hrat 25° C. The autoclave was vented to relieve the pressure and thecontents of the autoclave were transferred to a jar. The polymer wastaken up in methylene chloride and purified by precipitation into excessacetone. The precipitated polymer was dried in vacuo to give 2.77 g ofpolymer. The polymer displayed strong bands attributable to sulfonylgroup in the infrared (film on KBr plate) at 1160 and 1330 cm⁻¹.

Example 242 Copolymerizaton of Ethylene and Methyl Vinyl Ketone

[1188] Methyl vinyl ketone (MVK) was stirred over anhydrous K₂CO₃ andvacuum transferred using a high vacuum line to a dry flask containingphenothiazine (50 ppm). Ethylene and MVK (5 ml) were copolymerized usingthe procedure of Example 125 using as catalyst{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃)SbF₆ ⁻ (0.084 g, 0.10 mmol) togive 0.46 g of copolymer (0.38 g after correcting for catalyst residue).¹H NMR (CDCl₃): 0.75-0.95 (m, CH₃); 0.95-1.45 (m, CH and CH₂); 1.55 (m,—CH ₂CH₂C(O)CH₃); 2.15 (s, —CH₂CH₂C(O)CH ₃); 2.4 (t, —CH₂CH ₂C(O)CH₃).Based on the triplet at 2.15, it appeared that much of the ketonefunctionality was located on the ends of the hydrocarbon branches.Integration showed that the copolymer contained 2.1 mole % MVK, and has94 methyl carbon (exclusive of methyl ketones) per 1000 methyl carbonatoms. The turnover was 128 equivalents of ethylene and 3 equivalents ofMVK per Pd. GPC (THF, PMMA standard): Mn=5360, Mw=7470, Mw/Mn=1.39.

Example 243

[1189] 1-Hexene (20 ml) was polymerized in methylene chloride (10 ml)according to example 173 to give 4.22 g of viscous gel (1002 equivalents1-hexene per Pd). Integration of the ¹H NMR spectrum showed 95 methylcarbons per 1000 methylene carbons. ¹³C NMR quantitative analysis,branching per 1000 CH2: Total methyls (103), Methyl (74.9), Ethyl(nonedetected), Propyl (none detected), Butyl (12.4), Amyl (none detected),≧Hexyl and end of chains (18.1). Integration of the CH₂ peaks due to thestructure —CH(R)CH₂CH(R′)—, where R is an alkyl group, and R′is an alkylgroup with two or more carbons showed that in 74% of these structures,R═Me.

[1190] Listed below are the ¹³C NMR data upon which the above analysisis based. 13_(C) NMR data TCB, 140 C., 0.05M CrAcAc Freg ppm Intensity42.6359 4.05957 αα for Me & Et⁺ branches 37.8987 9.10141 MB₃ ⁺ 37.283364.4719 αB₁ 36.8537 8.67514 35.5381 4.48108 34.8803 4.30359 34.55145.20522 34.2755 21.6482 33.2411 4.13499 MB₁ 32.9811 32.0944 MB₁ 31.946714.0714 3B₆ ⁺, 3EOC 30.7212 5.48503 γ + γ + B, 3B₄ 30.2597 28.5961 γ +γ + B, 3B₄ 30.143 50.4726 γ + γ + B, 3B₄ 29.7717 248 γ + γ + B, 3B₄29.342 17.4732 γ + γ + B, 3B₄ 27.5702 27.2867 βγ for 2 Me branches27.1935 49.5612 βγ + B, (4B₅, etc.) 27.045 23.1776 23.0292 9.56673 2B₄22.6526 14.1631 2B₅ ⁺, 2EOC 20.2495 5.72164 1B₁ 19.7455 48.8451 1B₁13.9049 21.5008 1B₄+, 1EOC

Example 244

[1191] 1-Heptene (20 ml) was polymerized in methylene chloride (10 ml)according to example 173 to give 1.29 g of viscous gel (263 equivalents1-heptene per Pd). Integration of the ¹H NMR spectrum showed 82 methylcarbons per 1000 methylene carbons. ¹³C NMR quantitative analysis,branching per 1000 CH₂: Total methyls (85), Methyl (58.5), Ethyl(nonedetected), Propyl (none detected), Butyl (none detected), Amyl (14.1),≧Hexyl and end of chains (11.1). Integration of the CH₂ peaks due to thestructure —CH(R)CH₂CH(R′)—, where R is an alkyl group, and R′ is analkyl group with two or more carbons showed that in 71% of thesestructures, R═Me. DSC (two heats, −150-->150° C., 15° C./min) showsTg=−42° C. and a Tm=28° C. (45 J/g).

[1192] Listed below are the ¹³C NMR data upon which the above analysisis based. 13_(C) NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity42.6041 5.16375 αα for Me & Et⁺ 37.851 15.9779 MB₃ ⁺ 37.5963 7.6732237.2356 99.6734 αB1 35.4956 7.58713 34.8219 6.32649 34.6097 6.3769534.2278 37.6181 33.3418 3.78275 MB₁ 32.9228 60.7999 MB₁ 32.2809 13.624931.9148 21.2367 3B6⁺, 3EOC 30.5886 13.8482 γ + γ + B, 3B₄ 30.461322.1996 γ + γ + B, 3B₄ 30.2173 48.8725 γ + γ + B, 3B₄ 30.1059 80.2189γ + γ + B, 3B₄ 29.7292 496 γ + γ + B, 3B₄ 29.3049 26.4277 γ + γ + B, 3B₄27.1511 114.228 βγ^(+B) ₁ (4B₅, etc.) 27.0025 47.5199 26.7267 20.481724.5623 3.32234 22.6207 36.4547 2B₅ ⁺, 2EOC 20.2176 7.99554 1B₁ 19.708470.3654 1B₁ 13.8677 36.1098 1B₄ ⁺, EOC

Example 245

[1193] 1-Tetradecene (20 ml) was polymerized in methylene chloride (10ml) according to example 173 to give 6.11 g of sticky solid (622equivalents 1-tetradecene per Pd). Integration of the ¹H NMR spectrumshowed 64 methyl carbons per 1000 methylene carbons. ¹³C NMRquantitative analysis, branching per 1000 CH2: Total methyls (66),Methyl (35.2), Ethyl(5.6), Propyl (1.2), Butyl (none detected), Amyl(2.1),

[1194] ≧Hexyl and end of chains (22.8). Integration of the CH₂ peaks dueto the structure —CH(R)CH₂CH(R′)—, where R is an alkyl group, and R′ isan alkyl group with two or more carbons showed that in 91% of thesestructures, R═Me. The region integrated for the structure where both Rand R′ are ≧Ethyl was 40.0 ppm to 41.9 ppm to avoid including a methinecarbon interference.

[1195] Listed below are the ¹³C NMR data upon which the above analysisis based. 13_(C) NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity39.2826 6.684 MB₂ 37.8012 8.13042 MB₃ 37.2171 24.8352 αB₁, 3B₃ 34.169431.5295 αγ⁺B, (4B₄, 5B₅, etc.) MB₁ 33.6809 13.0926 αγ⁺B, (4B₄, 5B₅,etc.) MB₁ 32.9004 13.0253 MB₁ 31.9022 25.0187 3B₆+, 3EOC 30.1978 42.5593γ + γ + B, 3B₄ 30.0969 34.1982 γ + γ + B, 3B₄ 29.7252 248 γ + γ + B, 3B₄29.3004 26.4627 γ + γ + B, 3B₄ 27.1394 31.8895 βγ + B, 2B₂, (4B₅, etc.)26.9748 40.5922 βγ + B, 2B₂, (4B₅, etc.) 26.3642 7.06865 βγ + B, 2B₂,(4B₅, etc.) 22.6209 25.5043 2B₅ ⁺, 2EOC 19.6952 15.0868 1B₁ 13.875924.9075 1B₄+, 1EOC 10.929 7.63831 1B₂

Example 246

[1196] This example demonstrates copolymerization of ethylene and1-octene to give polymer with mostly C6+ branches. Under nitrogen,[(2,6-i-PrPh)₂DABH₂]NiBr₂ (0.005 g, 0.0084 mmol) and 9.6 wt. % MAO intoluene (0.50 mL) were dissolved in 10 mL of toluene at roomtemperature. The resulting solution was immediately transferred to a 100mL autoclave that had previously been flushed with nitrogen andevacuated. 1-Octene (40 mL, 255 mmol) was then added to the reactor,which was subsequently charged with ethylene (320 kPa). The reactionmixture was stirred for 60 min, during which time the temperature insidethe reactor varied between 24 and 28° C. Ethylene was then vented, andthe product polymer was precipitated by addition of the crude reactionmixture to 50 mL of methanol containing 5 mL of concentrated aqueousHCl. The polymer precipitated as a slightly viscous oil; this wasremoved by pipette and dried affording 3.03 g of amorphousethylene/1-octene copolymer. Branching per 1000 CH₂ was quantified by¹³C NMR (C₆D₃Cl₃, 25° C.): total Methyls (83.6), Methyl (4), Ethyl(1.6),Propyl (4.4), Butyl (5.6), Amyl (10.1), ≧Hex and end of chains (65.8),≧Am and end of chains (69.3), ≧Bu and end of chains (73.7). GPC(trichlorobenzene vs. linear polyethylene): M_(w)=48,200, M_(n)=17,000.DSC: Tg=−63° C.

Example 247

[1197] This example demonstrates copolymerization of ethylene and1-octene to give polymer with mostly methyl and C6+ branches. Undernitrogen, [(2,6-i-PrPh)₂DABH2]NiBr₂ (0.005 g, 0.0084 mmol) and 9.6 wt. %MAO in toluene (0.50 mL) were dissolved in 40 mL of toluene at −40° C.The resulting solution was immediately transferred to a 100 mL autoclavethat had previously been flushed with nitrogen and evacuated. 1-Octene(10 mL, 64 mmol) was then added to the reactor under 324 kPa ofethylene. The resulting reaction mixture was stirred under 324 kPa ofethylene for 1 h 10 min. During this time the temperature inside thereactor varied between 29 and 40° C. Ethylene was then vented, and theproduct polymer was precipitated by addition of the crude reactionmixture to methanol. The polymer was dried affording 6.45 g ofethylene/1-octene copolymer. Branching per 1000 CH₂ was quantified by¹³C NMR (C₆D₃Cl₃, 25° C.): Total methyls (50.7), Methyl (13.7),Ethyl(2.4), Propyl (3.5), Butyl (4.1), Amyl (1), ≧Hex and end of chains(26), ≧Am and end of chains (30.4), ≧Bu and end of chains (31). GPC(trichlorobenzene vs. linear polyethylene): M_(w)=116,000, M_(n)=9,570.

Example 248

[1198] Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) and(2,6-i-PrPh)₂DABMe₂ (0.024 g, 0.06 mmol) were dissolved in benzene (5.0mL). To the resulting solution was added HBAF⁻(Et₂O)₂ (0.060 g, 0.06mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂H₄ for 17.5 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=9.2 g. ¹H NMR(CDCl₂CDCl₂, 120° C.) showed that this sample contained 49 methyl-endedbranches per 1000 methylenes. DSC: Tm=118.8° C., ΔH_(f)=87.0 J/g.

Example 249

[1199] Under a nitrogen atmosphere, Ni[P(O-2-C₆H₄-Me)₃]₂(C₂H₄) (0.047 g,0.06 mmol) and (2,6-i-PrPh)₂DABMe₂ (0.024 g, 0.06 mmol) were dissolvedin benzene (5.0 mL). To the resulting solution was added HBAF⁻(Et₂O)₂(0.060 g, 0.06 mmol). The resulting solution was immediately frozeninside a 40 mL shaker tube glass insert. The glass insert wastransferred to a shaker tube, and its contents allowed to thaw under anethylene atmosphere. The reaction mixture was agitated under 6.9 MPaC₂H₄ for 18 h at ambient temperature. The final reaction mixturecontained polyethylene, which was washed with methanol and dried; yieldof polymer=8.9 g. ¹H NMR (CDCl₂CDCl₂, 120° C.) showed that this samplecontained 47 methyl-ended branches per 1000 methylenes. DSC: Tm=112.1°C., ΔH_(f)=57.5 J/g.

Example 250

[1200] A 100 mL autoclave was charged with a solution of Pd₂(dba)₃(dba=dibenzylideneacetone) (0.054 g, 0.059 mmol) in 40 mL of chloroform.A solution of (2,6-i-PrPh)₂DABMe₂¥HBAF⁻(Et₂O)₂ (0.085 g, 0.059 mmol)(see Example 256) in 10 mL of chloroform was then added under 2.1 MPa ofethylene. The reaction mixture was stirred for 3 h. During this time thetemperature inside the reactor varied between 24 and 40° C. Ethylene wasthen vented, and the product polymer was precipitated by addition of thecrude reaction mixture to methanol. The polymer was dried affording 14.7g of viscous polyethylene. ¹H NMR (CDCl₃, 25° C.) of this materialshowed it to be branched polyethylene with 115 methyl-ended branches per1000 methylenes. GPC analysis in trichlorobenzene gave M_(n)=97,300,M_(w)=225,000 vs. linear polyethylene.

Example 251

[1201] A 100 mL autoclave was charged with solid Pd(OAc)₂ (OAc=acetate)(0.027 g, 0.12 mmol) and (2,6-i-PrPh)₂DABMe₂ (0.049 g, 0.12 mmol). Thereactor was flushed with nitrogen and evacuated. A solution of 54 wt. %HBF₄¥Et₂O (0.098 g, 0.60 mmol) in 10 mL of chloroform was then addedunder 2.1 MPa of ethylene. The reaction mixture was stirred for 1.5 h.During this time, the temperature inside the reactor varied between 24and 37° C. Ethylene was then vented, and the product polymer wasprecipitated by addition of the crude reaction mixture to methanol. Thepolymer was dried affording 4.00 g of viscous polyethylene. ¹H NMR(CDCl₃, 25° C.) of this material showed it to be branched polyethylenewith 100 methyl-ended branches per 1000 methylenes. GPC analysis intrichlorobenzene gave M_(n)=30,500, M_(w)=43,300 vs. linearpolyethylene.

Example 252

[1202] (Note: It is believed that in the following experiment,adventitious oxygen was present and acted as a cocatalyst.) Undernitrogen, [(2.6-i-PrPh)₂ DAB An]Ni(COD) (0.006 g, 0.009 mmol) and 9.6wt. % MAO in toluene (0.54 mL, 1.66 mmol) were dissolved in 50 mL oftoluene. This mixture was then transferred to a 100 mL autoclave. Theautoclave was then charged with 2.1 MPa of ethylene. The reactionmixture was stirred for 8 min. During this time, the temperature insidethe reactor varied between 23 and 51° C. Ethylene pressure was thenvented. The product polymer was washed with methanol and dried,affording 8.44 g of polyethylene. ¹H NMR (CDCl₂, 120° C.) showed thatthis sample contained 77 methyl-ended branches per 1000 methylenes.

Example 253

[1203] Under nitrogen, [(2,4,6-MePh)DABAn]NiBr₂ (0.041 g, 0.065 mmol)was suspended in cyclopentene (43.95 g, 645 mmol). To this was added a 1M solution of EtAlCl₂ in toluene (3.2 mL, 3.2 mmol). The resultingreaction mixture was transferred to an autoclave, and under 700 kPa ofnitrogen heated to 60° C. The reaction mixture was stirred at 60° C. for18 h; heating was then discontinued. When the reactor temperature haddropped to −30° C., the reaction was quenched by addition ofisopropanol. The resulting mixture was stirred under nitrogen forseveral minutes. The mixture was then added under air to a 5% aqueousHCl solution (200 mL). The precipitated product was filtered off, washedwith acetone, and dried to afford 6.2 g of polycyclopentene as a whitepowder. DSC of this material showed a broad melting transition centeredat approximately 190° C. and ending at approximately 250° C.; ΔH_(f)=18J/g. Thermal gravimetric analysis of this sample showed a weight lossstarting at 184° C.: the sample lost 25% of its weight between 184 and470° C., and the remaining material decomposed between 470 and 500° C.

Example 254

[1204] Under nitrogen, [(2,6-Me-4-BrPh)₂DABMe₂]NiBr₂ (0.010 g, 0.015mmol) was suspended in cyclopentene (5.0 g, 73.4 mmol). To this wasadded a 1 M solution of EtAlCl₂ in toluene (0.75 mL, 0.75 mmol). Theresulting reaction mixture was stirred at room temperature for 92 h,during which time polycyclopentene precipitated. The reaction was thenquenched by addition of ˜5 mL of methanol under nitrogen. Several dropsof concentrated HCl was then added under air. The product was thenfiltered off, washed with more methanol followed by acetone, and driedto afford 1.31 g of polycyclopentene as a white powder. DSC of thismaterial showed a broad melting transition centered at approximately200° C. and ending at approximately 250° C.; ΔH_(f)=49 J/g. Thermalgravimetric analysis of this sample showed a weight loss starting at˜477° C.; the sample completely decomposed between 477 and 507° C.

Example 255

[1205] Under nitrogen, [(2,6-i-PrPh)₂DABMe₂]NiBr₂ (0.008 g, 0.015 mmol)was suspended in cyclopentene (5.00 g, 73.4 mmol). To this was added a 1M solution of EtAlCl2 in toluene (0.75 mL, 0.75 mmol). A magneticstirbar was added to the reaction mixture and it was stirred at roomtemperature; after 92 h at room temperature the reaction mixture couldno longer be stirred due to precipitation of polycyclopentene solids. Atthis point the reaction was then quenched by addition of ˜5 mL ofmethanol under nitrogen. Several drops of concentrated HCl was thenadded under air. The product was then filtered off, washed with moremethanol followed by acetone, and dried to afford 2.75 g ofpolycyclopentene as a white powder. DSC of this material showed a broadmelting transition centered at approximately 190° C. and ending atapproximately 250° C.; ΔH_(f)=34 J/g. Thermal gravimetric analysis ofthis sample showed a weight loss starting at ˜480° C.; the samplecompletely decomposed between 480 and 508° C.

Example 256

[1206] HBAF (0.776 mmol) was dissolved in 5 ml of Et₂O. A secondsolution of 0.776 mmol of (2,6-i-PrPh)₂DABMe₂ in 3 ml of Et₂O was added.The reaction turned deep red-brown immediately. After stirring for 2 hthe volatiles were removed in vacuo to give the protonated α-diiminesalt which was a red crystalline solid.

Example 257

[1207] HBF₄ (0.5 mmol) was dissolved in 4 ml of Et₂O. A second solutionof 0.5 mmol of (2,6-i-PrPh)₂DABMe₂ in 3 ml of Et₂O was added. A colorchange to deep red occurred upon mixing. The reaction was stirredovernight. The volatiles were removed in vacuo to give to give theprotonated α-diimine salt which was an orange solid.

Example 258

[1208] HO₃SCF₃ (0.5 mmol) was dissolved in 4 ml of Et₂O. A secondsolution of 0.5 mmol of (2,6-i-PrPh)₂DABMe₂ in 3 ml of Et₂O was added. Acolor change to deep red occurred upon mixing after a few minutes anyellow-orange precipitate began to form. The reaction was stirredovernight. The product, believed to be the protonated α-diimine salt,was isolated by filtration rinsed with Et₂O and dried in vacuo.

Example 259

[1209] HBAF (0.478 mmol) was dissolved in 5 ml of Et₂O. A secondsolution of 0.776 mmol of [(2,6-i-PrPh)N═C(CH₃)]₂CH₂ in 3 ml of Et₂O wasadded. The reaction was stirred overnight. Removal of the volatiles invacuo gave an off white solid, believed to be the protonated 1,3-diiminesalt.

Example 260

[1210] HBF₄ (0.478 mmol) was dissolved in 5 ml of Et₂O. A secondsolution of 0.478 mmol of [(2,6-i-PrPh)N═C(CH₃)]₂CH₂ in 3 ml of Et₂O wasadded , the reaction turned cloudy with a white precipitate. Thereaction was stirred overnight. The white solid, believed to be theprotonated 1,3-diimine salt, was isolated by filtration rinsed with Et₂Oand dried in vacuo.

Example 261

[1211] The product of Example 256 (78 mg) was dissolved in 20 ml oftoluene. The reaction vessel was charged with 140 kPa (absolute) ofethylene. A solution of 10 mg Ni(COD)₂ in 3 ml of toluene was added.Ethylene was added (138 kPa pressure, absolute) and the polymerizationwas run for 24 h at ambient temperature. Precipitation with MeOH gave157 mg of white spongy polyethylene.

Example 262

[1212] The product of Example 257 (27 mg) was dissolved in 20 ml oftoluene. The reaction vessel was charged with 35 kPa of ethylene. Asolution of 10 mg Ni(COD)₂ in 3 ml of toluene was added. Ethylene wasadded (138 kPa pressure, absolute) and the polymerization was run for 24h at ambient temperature. Precipitation with MeOH gave 378 mg of stickywhite polyethylene.

Example 263

[1213] The product of Example 258 (30 mg) was dissolved in 20 ml oftoluene. The reaction vessel was charged with 140 kPa (absolute) ofethylene. A solution of 10 mg Ni(COD)₂ in 3 ml of toluene was added.Ethylene was added (138 kPa pressure, absolute) and the polymerizationwas run for 24 h at ambient temperature. Precipitation with MeOH gave950 mg of amorphous polyethylene.

Example 264

[1214] To a burgundy slurry of 1 mmol of VCl₃ (THF)₃ in 10 ml of THF wasadded a yellow solution of 1 mmol of (2,6-i-PrPh)₂DABMe₂ in 4 ml of THF.After 10 minutes of stirring the reaction was a homogenous red solution.The solution was filtered to remove a few solids, concentrated and thencooled to −30° C. The red crystals that formed were isolated byfiltration, rinsed with pentane and dried in vacuo. The yield was 185mg.

Example 265

[1215] The product of Example 264 (6 mg) was dissolved in 20 ml oftoluene. The resulting solution was placed under 140 kPa (absolute) ofethylene. PMAO solution (0.8 mL, 9.6 wt % Al in toluene) was added andthe polymerization was stirred for 3 h. The reaction was halted by theaddition of 10% HCl/MeOH. The precipitated polymer was isolated byfiltration, washed with MeOH and dried in vacuo. The yield was 1.58 g ofwhite polyethylene.

Example 266

[1216] Lanthanide metal tris-triflates (wherein the lanthanide metalswere Y, La, Sm, Er, and Yb), 1 mmol, was slurried in 10 ml of CH₂Cl₂. Asolution of 1 mmol of (2,6-i-PrPh)₂DABMe₂ in 3 ml of CH₂Cl₂ was addedand the reaction stirred for 16 h at ambient temperature. The solutionwas filtered to give a clear filtrate. Removal of the solvent in vacuogave light yellow to orange powders.

Example 267

[1217] Each of the various materials (0.02 mmol) prepared in Example 266were dissolved in 20 ml of toluene. The resulting solutions were placedunder 140 kPa (absolute) of ethylene. MMAO-3A solution (1.0 mL, 6.4 wt %Al in toluene) was added and the polymerizations were stirred for 3 h.The reactions were halted by the addition of 10% HCl/MeOH. Theprecipitated polymers were isolated by filtration washed with MeOH anddried in vacuo. Polymer yields are shown the following table, LanthanideMetal Yield (g) Yb 0.117 La 0.139 Sm 0.137 Y 0.139 Er 0.167

Example 268

[1218] [(2,6-i-PrPh)₂DABMe₂]Ni-O₂ (68 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. PMAO (0.7 mL, 9.6 wt. % Al in toluene) was added and thepolymerization was conducted for 16 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 1.67 g of rubberypolyethylene.

Example 269

[1219] [(2,6-i-PrPh)₂DABMe₂]Ni-O₂ (65 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. PMAO (0.7 mL, 9.6 wt. % Al in toluene) was added and thepolymerization was conducted for 16 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 1.9 g of rubberypolyethylene.

Example 270

[1220] [(2,6-i-PrPh)₂DABMe₂]CrCl₂ ⁻ (THF) (15 mg) was dissolved in 20 mlof toluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 694 mg ofpolyethylene. DSC (−150 to 250° C. at 10° C./min) results from thesecond heating were T_(m) 129° C., ΔH_(f) 204 J/g.

Example 271

[1221] [(2,6-i-PrPh)₂DABMe₂]CrCl₃ (14 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 833 mg ofpolyethylene. DSC (−150 to 250° C. at 10° C./min) results from thesecond heating were T_(m) 133° C., ΔH_(f) 211 J/g.

Example 272

[1222] [(2,6-i-PrPh)₂DABMe₂]CrCl₂ ⁻ (THF) (14 mg) was dissolved in 20 mlof toluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 316 mg ofpolyethylene. DSC results from the second heating were (−150 to 250° C.at 10° C./min) T_(m) 133° C., ΔH_(f) 107 J/g.

Example 273

[1223] [(2,6-i-PrPh)₂DABMe₂]CrCl₃ (15 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 605 mg ofpolyethylene. DSC (−150 to 250° C. at 10° C./min) results from thesecond heating were T_(m) 134° C., ΔH_(f) 157 J/g.

Example 274

[1224] A 61 mg sample of {[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCHCl)]BAF wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration, washed withacetone and dried. The yield was 2.24 g of rubbery polyethylene.

Example 275

[1225] A 65 mg sample of {[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCHCl)]BAF wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration, washed withacetone and dried. The yield was 2.0 g of rubbery polyethylene.

Example 276

[1226] A 61 mg sample of {[(2,6-iPrPh)₂DABAn]Ni(η³-H₂CCHCH₂)}Cl wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration, washed withacetone and dried. The yield was 1.83 g of rubbery polyethylene.

Example 277

[1227] A 60 mg sample of {[(2,6-iPrPh)₂DABMe₂]Ni(η³-H₂CCHCH₂)}Cl wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration, washed withacetone and dried. The yield was 1.14 g of rubbery polyethylene.

Example 278

[1228]

[(2,6-i-PrPh)₂DAB(4-F-Ph)₂]NiBr₂

[1229] In a 250-mL RB flask fitted with pressure equalizing additionfunnel, thermometer, magnetic stirrer, and N₂ inlet was placed 0.75 g(3.0 mmol) of 4,4′-difluorobenzil, 13.8 mL (80 mmol) of2,6-diisopropylaniline (DIPA), and 100 mL dry benzene. In the additionfunnel was placed 50 mL of dry benzene and 2.0 mL (3.5 g; 18 mmol) oftitanium tetrachloride. The reaction flask was cooled to 2° C. with iceand the TiCl₄ solution was added dropwise over 45 min, keeping thereaction temperature below 5° C. The ice bath was removed after additionwas complete and the mixture was stirred at RT for 72 h. The reactionmixture was partitioned between water and ethyl ether, and the etherphase was rotovapped and the concentrated oil was washed with 800 mL 1NHCl to remove the excess diisopropylaniline. The mixture was extractedwith 100 mL of ether, and the ether layer was washed with water androtovapped. Addition of 15 mL hexane plus 30 mL of methanol to theconcentrate resulted in the formation of fine yellow crystals which werefiltered, methanol-washed, and dried under suction to yield 0.4 g of(2,6-i-PrPh)₂DAB(4-F-Ph)₂, mp: 155-158° C.

[1230] A 60-mg (0.092-mmol) sample of (2,6-i-PrPh)₂DAB(4-F-Ph)₂ wasstirred under nitrogen with 32 mg (0.103 mmol) of nickel(II)dibromide-dimethoxyethane complex in 20 mL of methylene chloride for 66h. The orange-brown solution was rotovapped and held under high vacuumfor 2 h to yield 86 mg of red-brown solids. The solid product wasscraped from the sides of the flask, stirred with 20 mL hexane, andallowed to settle. The yellow-orange hexane solution was pipetted offand the remaining solid was held under high vacuum to yield 48 mg of theorange-brown complex [(2,6-i-PrPh)₂DAB(4-F-Ph)₂]NiBr₂.

Example 279 Ethylene polymerization with[(2,6-i-PrPh)₂DAB(4-F-Ph)₂]NiBr₂

[1231] A 26-mg (0.033-mmol) sample of [(2,6-i-PrPh)₂DAB(4-F-Ph)₂]NiBr₂was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 25mL of dry toluene. Then 0.6 mL of polymethylalumoxane was injected,turning the orange-brown solution to a deep green-black solution. Themixture was pressurized immediately with ethylene to 152 kPa (absolute)and stirred at RT for 17 h. The reaction soon became warm to the touch;this heat evolution persisted for over an hour and the liquid volume inthe Schlenk flask was observed to be slowly increasing. After 17 h, thereaction was still dark green-brown, but thicker and significantly (20%)increased in volume. The ethylene was vented; the offgas contained about3% butenes (1-butene, 1.9%; t-2-butene, 0.6%; c-2-butene, 0.9%) by GC(30-m Quadrex GSQ Megabore column; 50-250° C. at 10°/min). The toluenesolution was stirred with 6N HCl/methanol and was separated; the toluenewas rotovapped and held under high vacuum to yield 9.53 g of low-meltingpolyethylene wax. There seemed to be significant low-boiling speciespresent, probably low-mw ethylene oligomers, which continued to boil offunder high vacuum. ¹H NMR (CDCl₃; 60° C.) of the product showed aCH₂:CH₃ ratio of 206:17, which is 57 CH₃'s per 1000 CH₂'s. There werevinyl peaks at 5-5.8 ppm; if the end groups are considered to be vinylsrather than internal olefins, the degree of polymerization was about 34.

Example 280 Synthesis of [(2-CF₃Ph)₂DABMe₂]NiBr₂

[1232]

[(2-CF₃Ph) 2DABMe₂]NiBr₂

[1233] A mixture of 10.2 mL (13.1 g; 81.2 mmol) 2-aminobenzotrifluorideand 3.6 mL (3.5 g; 41 mmol) freshly-distilled 2,3-butanedione in 15 mLmethanol containing 6 drops of 98% formic acid was stirred at 35° C.under nitrogen for 8 days. The reaction mixture was rotovapped and theresultant crystalline solids (1.3 g) were washed with carbontetrachloride. The crystals were dissolved in chloroform; the solutionwas passed through a short alumina column and evaporated to yield 1.0 gof yellow crystals of the diimine (2-CF₃Ph)₂DABMe₂. ¹H NMR analysis(CDCl₃): 2.12 ppm (s, 6H, CH3); 6.77 (d, 2H, ArH, J=9 Hz); 7.20 (t, 2H,ArH, J=7 Hz); 7.53(t, 2H, ArH, J=7 Hz); 7.68 (t, 2H, ArH, J=8 Hz).Infrared spectrum: 1706, 1651, 1603, 1579, 1319, 1110 cm⁻¹. Mp: 154-156°C.

[1234] A mixture of 0.207 g (0.56 mmol) of (2-CF₃Ph)₂DABMe₂ and 0.202 g(0.65 mmol) of nickel(II) dibromide-dimethoxyethane complex in 13 mL ofmethylene chloride was stirred at RT under nitrogen for 3 hr. Thered-brown suspension was rotovapped and held under high vacuum to yield0.3 g of [(2-CF₃Ph)₂DABMe₂]NiBr₂ complex.

Example 281 Ethylene polymerization with[(2-CF₃Ph)₂DABMe₂]NiBr₂

[1235] A 13-mg (0.022-mmol) sample of [(2-CF₃Ph)₂DABMe₂]NiBr₂ was placedin a Parr® 600-mL stirred autoclave; 200 mL of dry, deaerated hexane(dried over molecular sieves) was added and the hexane was saturatedwith ethylene by pressurizing to 450 kPa (absolute) ethylene andventing. Then 1.0 mL of modified methylalumoxane (1.7M in heptane;contains about 30% isobutyl groups) was injected into the autoclave withstirring, and the autoclave was stirred for 1 hr under 690 kPa(absolute) ethylene as the temperature rose from 20° C. to 61° C. overthe first 20 min and then slowly declined to 48° C. by the end of therun. The ethylene was vented and 3 mL of methanol was injected to stoppolymerization; the autoclave contained a white suspension of fineparticles of polyethylene; the appearance was like latex paint. Thepolymer suspension was added to methanol, and the polymer was stirredwith MeOH/HCl to remove catalyst. The suspension was filtered and driedin a vacuum oven (75° C.) to yield 26.8 g of fine, white powderypolyethylene Differential scanning calorimetry (15° C./min): Tg −45° C.;mp 117° C. (75 J/g). GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): Mn=2,350; Mw=8,640; Mz=24,400; Mw/Mn=3.67. Asolution of the polymer in chlorobenzene could be cast into a waxy filmwith little strength.

Example 282

[1236] Under nitrogen, Ni(COD)₂ (0.017 g, 0.062 mmol) and(2,4,6-MePh)₂DABAn (0.026 g, 0.062 mmol) were dissolved in 2.00 g ofcyclopentene to give a purple solution. The solution was then exposed toair (oxygen) for several seconds. The resulting dark red-brown solutionwas then put back under nitrogen, and EtAlCl₂ (1 M solution in toluene,3.0 mL, 3.0 mmol) added. A cranberry-red solution formed instantly. Thereaction mixture was stirred at room temperature for 3 days, duringwhich time polycyclopentene precipitated. The reaction was then quenchedby the addition of methanol followed by several drops of concentratedHCl. The reaction mixture was filtered, and the product polymer washedwith methanol and dried to afford 0.92 g of polycyclopentene as anoff-white powder. Thermal gravimetric analysis of this sample showed aweight loss starting at 141° C.: the sample lost 18% of its weightbetween 141 and 470° C., and the remaining material decomposed between470 and 496° C.

Example 283

[1237] Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) andthe ligand shown below (0.025 g, 0.06 mmol) were dissolved in benzene(5.0 mL). To the resulting solution was added HBAF⁻(Et₂O)₂ (0.060 g,0.06 mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂H₄ for 18 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=11.0 g.

Example 284

[1238] The catalyst {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻(0.025 g, 0.03 mmol) and CH₂═CH(CH₂)₆C₁₀F₂₁ (4.74 g, 7.52 mmol) weredissolved in 20 mL CH₂Cl₂ in a Schlenk flask in a drybox. The flask wasconnected to a Schlenk line and the flask was then briefly evacuated andrefilled with ethylene from the Schlenk line. This was stirred at RTunder 1 atm of ethylene for 72 hr. Solvent was evaporated to almostdryness. Acetone (70 mL) was added and the mixture was stirredvigorously overnight. The upper layer was decanted. The resulting yellowsolid was washed with 3×15 mL acetone, vacuum dried, and 1.15 g ofproduct was obtained. ¹H NMR analysis (CD₂Cl₂): 105 methyls per 1000methylene carbons. Comparison of the integral of the CH₂R_(f)(2.10 ppm)with the integrals of methyls(0.8-1.0 ppm) and methylenes(1.2-1.4 ppm)indicated a comonomer content of 6.9 mol %. The polymer exhibited aglass transition temperature of −55° C.(13 J/g) and a melting point of57° C. by differential scanning calorimetry. Gel permeationchromatography (THF, polystyrene standard): Mw=39,500, Mn=34,400,P/D=1.15.

Example 285

[1239] In a 100 mL Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.012 g,0.017 mmol) and CH₂═CH(CH₂)₆C₁₀F₂₁ (4.62 g, 7.33 mmol) were dissolved in32 mL of toluene under stirring. This was pressured with 1 atm ethyleneand was allowed to stir at 0° C. for 15 minutes. MAO (1.7 mL, 8.9 wt %in toluene) was added. This was allowed to vigorously stir at RT for 30min. Sixty mL methanol was then added. The white solid was filtered,followed by 3×30 ml 3:1 methanol/toluene wash, vacuum dried, and 3.24 gof white polymer was obtained. ¹H NMR analysis(o-dichlorobenzene-d₄,135° C.): 64 methyls per 1000 methylene carbons.Comparison of the integral of the CH₂R_(f) (2.37 ppm) with the integralsof methyls (1.1-1.2 ppm) and methylenes (1.4-1.8 ppm) indicated acomonomer content of 8.7 mol %. Mw=281,157, Mn=68,525, P/D=4.1.

Example 286

[1240] In a 100 mL Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.012 g,0.017 mmol) and CH₂═CH(CH₂)₆C₁₀F₂₁ (4.62 g, 7.33 mmol) were dissolved in32 mL of toluene under stirring. This was allowed to stir at 0° C. for15 minutes. MAO (1.7 mL, 8.9 wt % in toluene) was added. This wasallowed to stir at 0° C. for 2.5 h and then RT for 3 h. Methanol (200mL) was then added, followed by 1 mL conc. HCl. The white solid wasfiltered and washed with methanol, vacuum dried, and 0.79 g of whitesolid polymer was obtained. By differential scanning calorimetry, Tm 85°C.(22 J/g).

Example 287

[1241] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.0205 g,0.024 mmol) and CH₂═CH(CH₂)₄(CF₂)₄O(CF₂)₂SO₂F (3.5 g, 7.26 mmol) weredissolved in 18 mL CH₂Cl₂ in a Schlenk flask in a drybox. The flask wasconnected to a Schlenk line and the flask was then briefly evacuated andrefilled with ethylene from the Schlenk line. This was stirred at RTunder 1 atm of ethylene for 72 hr. Solvent was evaporated afterfiltration. The viscous oil was dissolved in 10 mL CH₂Cl₂, followed byaddition of 100 mL methanol. The upper layer was decanted. The reverseprecipitation was repeated two more time, followed by vacuum drying toyield 3.68 g of a light yellow viscous oil. ¹H NMR analysis (CDCl₃): 89methyls per 1000 methylene carbons. Comparison of the integral of theCH₂CF₂— (2.02 ppm) with the integrals of methyls(0.8-1.0 ppm) andmethylenes(1.1-1.4 ppm) indicated a comonomer content of 8.5 mol %. ¹⁹FNMR (CDCl₃): 45.27 ppm, —SO₂F; −82.56 ppm, −83.66 ppm, −112.82 ppm,−115.34 ppm, −124.45 ppm, −125.85 ppm, CF₂ peaks. The polymer exhibiteda glass transition temperature of −57° C. by differential scanningcalorimetry. Gel permeation chromatography (THF, polystyrene standard):Mw=120,000, Mn=78,900, P/D=1.54. The turnover numbers for ethylene andthe comonomer are 2098 and 195, respectively.

Example 288

[1242] In a 100 mL Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.017 g,0.024 mmol) and CH₂═CH (CH₂)₄(CF₂)₄O(CF₂)₂SO₂F (5.0 g, 10 mmol) weredissolved in 25 mL of toluene under stirring. MAO (2.3 mL, 8.9 wt % intoluene) was added. This was allowed to stir at RT for 15 hr. Sixty mLmethanol was then added, followed by 1 mL conc. HCl. The upper layer wasdecanted, residue washed with methanol (5×5 mL), vacuum dried, and 1.20g of a white viscous oil was obtained. ¹⁹F NMR (Hexafluorobenzene, 80°C.): 45.20 ppm, —SO₂F; −81.99 ppm, −82.97 ppm, −112.00 ppm, −114.36 ppm,−123.60 ppm, −124.88 ppm, CF₂ peaks.

Example 289

[1243] In a Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.012 g, 0.017mmol) and CH₂═CH(CH₂)₄(CF₂)₄O(CF₂)₂SO₂F (3.26 g, 6.77 mmol) weredissolved in 35 mL of toluene under stirring. This was pressured with 1atm ethylene and was allowed to stir at 0° C. for 15 minutes. MAO (1.7mL, 8.9 wt % in toluene) was added. This was allowed to vigorously stirat RT for 45 minutes. Methanol (140 mL) was then added, followed byaddition of 1 mL of conc. HCl. The white solid was filtered, followed bymethanol wash, vacuum dried to obtain 2.76 g of a white rubbery polymer.¹H NMR analysis (o-dichlorobenzene-d₄, 100° C.): 98 methyls per 1000methylene carbons. Comparison of the integral of the —CH₂CF₂— (2.02 ppm)with the integrals of methyls (0.8-1.0 ppm) and methylenes (1.1-1.4 ppm)indicated a comonomer content of 3.5 mol %. ¹⁹F NMR((0-dichlorobenzene-d₄): 45.19 ppm, —SO₂F; −82.70 ppm, −83.72 ppm,−112.96 ppm, −115.09 ppm, −124.37 ppm, −125.83 ppm, CF₂ peaks. Thepolymer exhibited Tm of 97° C. by differential scanning calorimetry.Mw=156,000, Mn=90,000, P/D=1.73.

Example 290

[1244] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.030 g, 0.035mmol) and CH₂═CH(CH₂)₄(CF₂)₂CO₂Et (3.0 g, 11.7 mmol) were dissolved in20 mL CH₂Cl₂ in a Schlenk flask in a drybox. The flask was connected toa Schlenk line and the flask was then briefly evacuated and refilledwith ethylene from the Schlenk line. This was stirred at RT under 1 atmof ethylene for 72 h. Solvent was evaporated. The viscous oil wasdissolved in 10 mL acetone, followed by addition of 60 mL methanol. Themixture was centrifuged. The upper layer was decanted. The oil wasdissolved in 10 mL acetone followed by addition of 60 mL methanol. Themixture was centrifuged again. The viscous oil was collected, and vacuumdried to obtain 1.50 g of a light yellow viscous oil. ¹H NMR analysis(CDCl₃): 67 methyls per 1000 methylene carbons. Comparison of theintegral of the CH₂CF₂— (2.02 ppm) with the integrals of methyls(0.8-1.0ppm) and methylenes(1.1-1.4 ppm) indicated a comonomer content of 11 mol%. The polymer exhibited a Tg of −61° C. by DSC. GPC (THF, polystyrenestandard): Mw=73,800, Mn=50,500, P/D=1.46.

Example 291

[1245] In a Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.019 g, 0.026mmol) and CH₂═CH(CH₂)₄(CF₂)₂CO₂Et (3.0 g, 11.7 mmol) were dissolved in35 mL of toluene. This was placed under 1 atm of ethylene at 0° C. for15 minutes. MAO (2.6 mL, 8.9 wt % in toluene) was added. This wasallowed to vigorously stir at 0° C. for 30 minutes. Methanol (120 mL)was then added, followed by 1 mL conc. HCl. The solid was filtered,washed with methanol and hexane, and vacuum dried to yield 1.21 g of awhite rubbery solid. ¹H NMR analysis (TCE-d₂, 110° C.): Comparison ofthe integral of the CH₂CF₂— (2.06 ppm) with the integrals ofmethyls(0.8-1.0 ppm) and methylenes(l.1-1.4 ppm) indicated a comonomercontent of 6.0 mol %. The polymer exhibited a Tg of −46° C. and Tm's at40° C. and 82° C. by DSC.

Example 292

[1246] In a Schlenk flask, [(2,6-i-PrPh)₂DABAn]NiBr₂ (0.022 g, 0.030mmol) and CH₂═CH(CH₂)₄(CF₂)₂CO₂Et (3.5 g, 13.7 mmol) were dissolved in30 mL of toluene. This was placed under nitrogen at 0° C. for 15minutes. MAO (3.0 mL, 8.9 wt % in toluene) was added. This was allowedto stir at 0° C. for 2.5 h and then RT for 6 h. Fifty mL methanol wasthen added, followed by 1 mL conc. HCl. The mixture was washed with 3×60mL water. The organic layer was isolated and dried by using Na₂SO₄.Evaporation of toluene and addition of hexane resulted in precipitationof an oil. The oil was washed with hexane another two times, and vacuumdried to yield 0.16 g of a yellow oil. Mw=35,600, Mn=14,400, P/D=2.47.

Example 293

[1247] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.0848 g, 0.1mmol) and CH₂═CH(CH₂)₄(CF₂)₂O(CF₂)₂SO₂F (11.5 g, 0.03 mol) weredissolved in 72 mL CH₂Cl₂ in a Schlenk flask in a drybox. The flask wasconnected to a Schlenk line and the flask was then briefly evacuated andrefilled with ethylene from the Schlenk line. This was stirred at RTunder 1 atm of ethylene for 72 hr. The solution was filtered throughCelite and then concentrated to 70 mL. Methanol (400 mL) was added understirring. The upper layer was decanted. The oil was redissolved in 70 mLCH₂Cl₂ followed by addition of 350 mL methanol. The viscous oil wascollected, vacuum dried and 24.1 g of a light yellow viscous oil wasobtained. ¹H NMR analysis (CDCl₃): 113 methyls per 1000 methylenecarbons. Comparison of the integral of the CH₂CF₂— (2.0 ppm) with theintegrals of methyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicateda comonomer content of 2.9 mol %. The polymer exhibited a Tg of −66° C.by DSC. GPC (THF, polystyrene standard): Mw=186,000, Mn=90,500,P/D=2.06. The turnover numbers for ethylene and the comonomer are 6,122and 183, respectively.

Examples 294-300

[1248] All of these Examples were done under 1 atm ethylene with a MAconcentration of 1.2M and {[(diimine)PdMe(Et₂O)]⁺SbF₆ ⁻) concentrationof 0.0022M at RT for 72 hr. Results are shown in the Table below. Ex.No. Diimine MA (mol %)* Mn P/D 294 (2,6-i- 6 12,300 1.8 PrPh)₂DABMe₂ 295(2,6-EtPh)₂DABMe₂ 16 7,430 1.9 296 (2,4,6- 23 2,840 2.1 MePh)₂DABMe₂ 297(2,4,6-MePh)₂DABAn 37 1,390 1.4 298 (2,4,6-MePh)₂DABH₂ 46 1,090 3.1 299(2-i-PrPh)₂DABMe₂ 17 410 ** 300 (2-MePh)₂DABMe₂ 29 320 **

Example 301

[1249] {[(2,6-EtPh)₂DABMe₂]PdCH₃(Et₂O)}⁺SbF₆ ⁻ (0.0778 g, 0.10 mmol) andmethyl acrylate (4.78 g, 0.056 mol) were dissolved in 40 mL CH₂Cl₂ in aSchlenk flask in a drybox. The flask was connected to a Schlenk line andthe flask was then briefly evacuated and refilled with ethylene from theSchlenk line. This was stirred at RT under 1 atm of ethylene for 72 h.The mixture was filtered through silica gel, solvent was evaporated andthen vacuum dried, and 1.92 g light of a yellow viscous oil wasobtained. ¹H NMR analysis (CDCl₃): 69 methyls per 1000 methylenecarbons. Comparison of the integral of the methyl on the ester groups(2.3 ppm) with the integrals of carbon chain methyls(0.8-1.0 ppm) andmethylenes(1.1-1.4 ppm) indicated a comonomer content of 16 mol %. Thepolymer exhibited a Tg of −68° C. by DSC. GPC (THF, polystyrenestandard): Mw=14,300, Mn=7,430, P/D=1.93.

Example 302

[1250] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.254 g, 0.30mmol) and CH₂═CHCO₂CH₂(CF₂)₆CF₃ (90.2 g, 0.20 mol) were dissolved in 150mL CH₂Cl₂ in a flask in the drybox. The flask was connected to a Schlenkline and the flask was then briefly evacuated and refilled with ethylenefrom the Schlenk line. This was stirred at RT under 1 atm of ethylenefor 24 h. The solution was decanted to 1200 mL methanol, resultedformation of oil at the bottom of the flask. The upper layer wasdecanted, oil dissolved in 150 mL CH₂Cl₂, followed by addition of 1200mL of methanol. The upper layer was decanted, oil dissolved in 600 mLhexane and filtered through Celite®. Solvent was evaporated, and thenvacuum dried, yielding 54.7 g of a viscous oil. ¹H NMR analysis (CDCl₃):99 methyls per 1000 methylene carbons. Comparison of the integral of theCH₂CF₂— (4.56 ppm) with the integrals of methyls(0.8-1.0 ppm) andmethylenes(1.1-1.4 ppm) indicated a comonomer content of 5.5 mol %. Thepolymer exhibited a Tg of −49° C. by DSC. Mw=131,000, Mn=81,800.

Example 303

[1251] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.169 g, 0.20mmol) and β-hydroxyethyl acrylate (6.67 g, 0.057 mol) were dissolved in40 mL CH₂Cl₂ in a flask in the drybox. The flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. This was stirred at RT under 1 atm ofethylene for 45 h. Solvent was evaporated. The residue was dissolved in100 mL hexane, followed by addition of 400 mL methanol. Upon standingovernight, a second upper layer formed and was decanted. The oil wasdissolved in 60 mL THF, followed by addition of 300 mL water. The upperlayer was decanted. The residue was dissolved in 100 mL 1:1CH₂Cl₂/hexane. This was filtered through Celite®. The solvent wasevaporated, vacuum dried and 6.13 g of a light yellow oil was obtained.¹H NMR analysis (CD₂Cl₂): 142 methyls per 1000 methylene carbons.Comparison of the integral of the CH₂CO₂— (2.30 ppm) with the integralsof methyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicated acomonomer content of 2.6 mol %. Mw=53,100, Mn=37,900, P/D=1.40.

Example 304

[1252] {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻ (0.169 g, 0.20mmol) and hydroxypropyl acrylate (7.52 g, 0.058 mol) were dissolved in40 mL CH₂Cl₂ in a flask in the drybox. The flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. This was stirred at RT under 1 atm ofethylene for 72 h. Solvent was evaporated. Eighty mL methanol was addedto dissolve the residue, followed by 250 mL water. The upper layer wasdecanted. The reverse precipitation was repeated one more time. The oilwas isolated, vacuum dried, and 1.1 g of a light yellow oil wasobtained. ¹H NMR analysis (CD₂Cl₂): 94 methyls per 1000 methylenecarbons. Comparison of the integral of the CH₂CO₂— (2.30 ppm) with theintegrals of methyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicateda comonomer content of 6.5 mol %. Mw=39,200, Mn=28,400, P/D=1.38.

Example 305

[1253] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.0141 g, 0.025 mmol). Cyclopentene was added (3.41g, 2,000 equivalents/Ni). A solution of MMAO (Akzo Nobel MMAO-3A,modified methylaluminoxane, 25% isobutyl groups in place of methylgroups) was added while stirring (0.75 ml, 1.7 M Al in heptane, 50equivalents/Ni). Following addition of the MMAO, the solution washomogeneous. After stirring for several hours, solid polymer started toprecipitate. After stirring for 46 hours, the solution was filtered andthe solids were washed several times on the filter with pentane. Thepolymer was dried in vacuo for 12 hours at room temperature to yield0.66 g polymer (388 turnovers/Ni). The polymer was pressed at 292° C. togive a transparent, light gray, tough film. DSC (25 to 300° C., 15°C./min, second heat): Tg=104° C., Tm (onset)=210° C., Tm (end)=285;C,Heat of fusion=14 J/g. X-ray powder diffraction shows peaks atd-spacings 5.12, 4.60, 4.20, 3.67, and 2.22. Error! Reference source notfound.¹H NMR (500 MHz, 155° C., d₄-o-dichlorobenzene, referenced todownfield peak of solvent=7.280 ppm): 0.923 (bs, 1.0H, —CHCH ₂CH—);1.332 (bs, 2.0H, —CHCH ₂CH ₂CH—); 1.759 (bs, 4.0H, —CHCH ₂CH ₂CH— and—CHCH₂CH₂CH—); 1.947 (bs, 1.0 H, —CHCH ₂CH—). The assignments are basedupon relative integrals and ¹H—¹³C correlations determined by 2D NMR.This spectrum is consistent with an addition polymer with cis-1,3enchainment of the cyclopentene.

Example 306

[1254] Cyclopentene was polymerized by [(2,4,6-MePh)₂DABMe₂]PdMeCl andMMAO according to Example 305 to give 0.37 g polymer (217 turnovers/Pd).The polymer was pressed at 250° C. to give a transparent, light brown,tough film. DSC (25 to 300° C., 15° C./min, second heat): Tg=84° C.,Tm(onset)=175° C., Tm (end)=255° C., Heat of fusion=14 J/g. ¹H NMR (400MHz, 120° C., d₄-o-dichlorobenzene, referenced to downfield peak ofsolvent=7.280 ppm): 0.90 (bs, 1H, —CHCH ₂CH—); 1.32 (bs, 2H, —CHCH ₂CH₂CH—); 1.72, 1.76 (bs, bs 4H, —CHCH ₂CH ₂CH— and —CHCH₂CH₂CH—); 1.94(bs, 1H, —CHCH ₂CH—). The assignments are based upon relative integralsand ¹H—¹³C correlations determined by 2D NMR. This spectrum isconsistent with an addition polymer with cis-1,3 enchainment of thecyclopentene.

Example 307

[1255] Cyclopentene was polymerized by [(2,6-EtPh)₂DABMe₂]PdMeCl andMMAO according to Example 305 to give 0.39 g polymer (229 turnovers/Pd).The polymer was pressed at 250° C. to give a transparent, light brown,tough film. DSC (25 to 300° C., 15° C./min, second heat): Tg=88° C.,Tm(onset)=175° C., Tm (end)=255° C., Heat of fusion=16 J/g. ¹H NMR (300MHz, 120° C., d₄-o-dichlorobenzene) is very similar to the spectrum ofExample 306.

Example 308

[1256] Cyclopentene was polymerized by [(2,4,6-MePh)₂DABMe₂]NiBr₂ andMMAO according to Example 305 to give 0.36 g polymer (211 turnovers/Ni).The polymer was pressed at 250° C. to give a transparent, colorless,tough film. DSC (25 to 300° C., 15° C./min, second heat): Tg=98° C.,Tm(onset)=160° C., Tm (end)=260° C., Heat of fusion=22 J/g. ¹H NMR (500MHz, 120° C., d₄-o-dichlorobenzene) is very similar to the spectrum ofExample 306. X-ray powder diffraction shows the same crystalline phaseas observed in Example 305.

Example 309

[1257] Cyclopentene was polymerized by [(2,6-i-PrPh)₂DABMe₂]PdMeCl andMMAO according to Example 305 to give 0.73 g of fine powder (429turnovers/Pd). The polymer was pressed at 250° C. to give a transparent,light brown tough film. DSC (25 to 300° C., 15° C/min, second heat):Tg=96° C., Tm(onset)=175° C., Tm (end)=250° C., Heat of fusion=14 J/g.¹H NMR (400 MHz, 120° C., d₄-o-dichlorobenzene) is very similar to thespectrum of Example 306. X-ray powder diffraction shows the samecrystalline phase as observed in Example 305.

Example 310

[1258] Cyclopentene was polymerized by [(2,6-i-PrPh)₂DABMe₂]PdCl₂ andMMAO according to Example 305 to give 0.856 g polymer (503turnovers/Pd). The polymer was pressed at 250° C. to give a transparent,light brown, tough film. DSC (25 to 300° C., 15° C./min, second heat):Tg=104° C., Tm(onset)=140° C., Tm (end)=245° C., Heat of fusion=19 J/g.¹H NMR (400 MHz, 120° C., d₄-o-dichlorobenzene) is very similar to thespectrum of Example 306.

Example 311

[1259] Cyclopentene was polymerized by [(2,6-EtPh)₂DABMe₂]NiBr₂ and MMAOaccording to Example 305 to give 0.076 g polymer (45 turnovers/Ni). ¹HNMR (400 MHz, 120° C., d₄-o-dichlorobenzene) is very similar to thespectrum of Example 306.

Example 312

[1260] Cyclopentene was polymerized by [(2,4,6-MePh)₂DABH₂]NiBr₂ andMMAO according to Example 305 to give 0.66 g polymer (388 turnovers/Ni).The polymer was pressed at 292° C. to give a tough film. ¹H NMR (400MHz, 120° C., d₄-o-dichlorobenzene) is very similar to the spectrum ofExample 306. A DSC thermal fractionation experiment was done in which asample was heated to 330° C. at 20° C./minute followed by stepwiseisothermal equilibration at the followed temperatures (times): 280° C.(6 hours) , 270° C. (6 hours) , 260° C. (6 hours), 250° C. (6 hours),240° C. (4 hours), 230° C. (4 hours), 220° C. (4 hours), 210° C. (4hours), 200° C. (3 hours), 190° C. (3 hours) , 180° C. (3 hours), 170°C. (3 hours), 160° C. (3 hours), 150° C. (3 hours). The DSC of thissample was then recorded from 0° C.-330° C. at 10° C./min. Tg=98° C., Tm(onset)=185° C., Tm (end)=310° C., Heat of fusion=35 J/g.

Example 313

[1261] Cyclopentene was polymerized by [(2-PhPh)₂DABMe₂]NiBr₂ and MMAOaccording to Example 305 to give 1.24 g polymer (728 turnovers/Ni). Thepolymer was pressed at 292° C. to give a transparent, light gray,brittle film. DSC (25 to 320° C., 10° C./min, second heat):Tm(onset)=160° C., Tm (end)=285° C., Heat of fusion=33 J/g. ¹H NMR (400MHz, 120° C., d₄-o-dichlorobenzene) is very similar to the spectrum ofExample 306. Several peaks attributed to cyclopentenyl end groups wereobserved in the range 5.2-5.7 ppm. Integration of these peaks was usedto calculate Mn=2130. IR (pressed film, cm⁻¹): 3050 (vw, olefinic endgroup, CH stretch), 1615(vw, olefinic end group, cis-CH═CH— double bondstretch), 1463(vs), 1445(vs), 1362(s), 1332(s), 1306(s), 1253(m),1128(w), 1041(w), 935(m), 895(w), 882(w), 792(w), 721(w, olefinic endgroup, cis-CH═CH—, CH bend). GPC (Dissolved in 1,2,4-trichlorobenzene at150° C., run at 100° C. in tetrachloroethylene, polystyrenecalibration): Peak MW=13,900; M_(n)=10,300; M_(w)=17,600;M_(w)/M_(n)=1.70.

Example 314

[1262] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.032 g, 0.050 mmol). Toluene (2.35 ml ) andcyclopentene (6.81 g, 2,000 equivalents/Ni) were added, followed byC₆H₅NHMe₂ ⁺ B(C₆F₅)₄ ⁻ (0.04 g, 50 equivalents/Ni). A solution of Et₃Alwas added while stirring (2.5 ml, 1 M in heptane, 50 equivalents/Ni).After stirring for 46 hours, the solution was filtered and the solidswere washed several times on the filter with pentane. The polymer wasdried in vacuo for 12 hours at room temperature to yield 0.16 g of finepowder (47 turnovers/Ni). A control experiment with no C₆H₅NHMe₂ ⁺B(C₆F₅)₄ ⁻ gave no polymer.

Example 315

[1263] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.032 g, 0.050 mmol). Toluene (3.46 ml ) andcyclopentene (6.81 g, 2,000 equivalents/Ni) were added. A solution ofEt₂AlCl was added while stirring (1.39 ml, 1.8 M in toluene, 50equivalents/Ni). After stirring for 46 hours, the solution was filteredand the solids were washed several times on the filter with pentane. Thepolymer was dried in vacuo for 12 hours at room temperature to yield0.53 g of fine powder (156 turnovers/Ni).

Example 316

[1264] The complex [(2,4,6-MePh)₂DABMe₂]NiBr₂ was weighed into a glassvial in the dry box (0.0070 g, 0.0130 mmol). Pentane (2.2 ml ) andcyclopentene (10.0 g, 11,300 equivalents/Ni) were added. A solution ofEtAlCl₂ was added while stirring (0.73 ml, 1.0 M in hexanes, 56equivalents/Ni). After stirring for 192 hours, the solution was filteredand the solids were washed several times on the filter with pentane. Thepolymer was dried in vacuo for 12 hours at room temperature to yield2.66 g of fine powder (3010 turnovers/Ni). The polymer was mixed with200 ml of MeOH in a blender at high speed to produce a fine powder. Thesolid was collected by filtration and then mixed for 1 hour with 39 mlof a 1:1 mixture of MeOH/concentrated aqueous HCl. The solid wascollected by filtration, washed with distilled water, and then washed onthe filter 3× with 20 ml of a 2 wt. % solution of Irganox® 1010 inacetone. The polymer was dried in vacuo for 12 hours at roomtemperature. DSC (25 to 300° C., 10° C./min, controlled cool at 10°C./min, second heat): Tg=98° C., Tm(onset)=160° C., Tm (end)=240° C.,Heat of fusion=17 J/g. TGA(air, 10° C./min): T(onset of loss)=330° C.T(10% loss)=450° C. ¹³C NMR (500 MHz ¹H frequency, 3.1 ml of1,2,4-trichlorobenzene, 0.060 g Cr(acac)₃, 120° C.): 30.640 (s, 2C),38.364 (s, 1C), 46.528 (s, 2C). This spectrum is consistent with anaddition polymer of cyclopentene with cis-1,3-enchainment. A sample ofthe polymer was melted in a Schlenk tube under a nitrogen atmosphere.Fibers were drawn from the molten polymer using a stainless steelcannula with a bent tip. A nitrogen purge was maintained during thefiber drawing. The fibers were tough and could be drawn about 2× bypulling against a metal surface heated to 125° C.

Example 317

[1265] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g,10,000 equivalents/Ni) was added. A solution of EtAlCl₂ was added whilestirring (0.73 ml, 1.0 M in hexanes, 50 equivalents/Ni). After stirringfor 168 hours, the solution was filtered and the solids were washedseveral times on the filter with pentane. The polymer was dried in vacuofor 12 hours at room temperature to yield 4.66 g of fine powder (4660turnovers/Ni). The polymer was mixed with 200 ml of MeOH in a blender athigh speed to produce a fine powder. The solid was collected byfiltration and then mixed for 1 hour with 39 ml of a 1:1 mixture ofMeOH/concentrated aqueous HCl. The solid was collected by filtration,washed with distilled water, and then washed on the filter 3× with 20 mlof a 2 wt. % solution of Irganox 1010 in acetone. The polymer was driedin vacuo for 12 hours at room temperature. DSC (25 to 350° C., 15°C./min, second heat): Tg=97° C., Tm(onset)=160° C., Tm (end)=285° C.,Heat of fusion=25 J/g. ¹³C NMR (500 MHz ¹H frequency, 3.1 ml of1,2,4-trichlorobenzene, 0.060 g Cr(acac)₃, 12° C.): 30.604 (s, 2C) ,38.333 (s, 1C), 46.492 (s, 2C). This spectrum is consistent with anaddition polymer of cyclopentene with cis-1,3-enchainment. A sample ofthe polymer was melted in a Schlenk tube under a nitrogen atmosphere.Fibers were drawn from the molten polymer using a stainless steelcannula with a bent tip. A nitrogen purge was maintained during thefiber drawing. The fibers were tough and could be drawn about 2× bypulling against a metal surface heated to 125° C. GPC (Dissolved in1,2,4-trichlorobenzene at 150° C., run at 100° C. intetrachloroethylene, polystyrene calibration): Peak MW=137,000;M_(n)=73,000; M_(w)=298,000; M_(w)/M_(n)=4.08.

Example 318

[1266] The complex {[(2,6-i-PrPh)₂DABMe₂]PdMe(Et₂O)}⁺SbF₆ ⁻ (0.05 g,0.060 mmol) was added to 10.0 g of stirring cyclopentene. Solid polymerformed rapidly and precipitated. The polymer was isolated by filtration,washed on the filter 3× with pentane, and dried in vacuo at roomtemperature to give 1.148 g finely divided powder (282 turnovers/Pd).DSC (25 to 350° C., 15° C./min, first heat): Tm(onset)=175° C., Tm(end)=245° C., Heat of fusion=16 J/g.

Example 319

[1267] The complex {[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻(0.05 g, 0.059 mmol) was added to 10.0 g of stirring cyclopentene. Thecomplex is not very soluble in cyclopentene. The amount of solidsincreased slowly. After 27 days, the solid polymer was isolated byfiltration, washed on the filter 3× with pentane, and dried in vacuo atroom temperature to give 1.171 g finely divided powder (292turnovers/Pd). DSC (25 to 350° C., 15° C./min, first heat):Tm(onset)=170° C., Tm (end)=255° C., Heat of fusion=24 J/g.

Example 320

[1268] The complex [(2,6-i-PrPh)₂DABMe₂]NiBr₂ was weighed into a glassvial in the dry box (0.025 g, 0.040 mmol). Cyclopentene (10.0 g, 1,000equivalents/Ni) was added. A solution of MMAO was added while stirring(0.802 ml, 2.5 M in heptane, 50 equivalents/Ni). After stirring for 5minutes, the mixture was rusty brown and still contained some solids. Anadditional 50 equivalents of MMAO were added and the solution becamehomogeneous. After 12 hours, the mixture was filtered and the solidswere washed several times on the filter with pentane. The polymer wasdried in vacuo for 12 hours at room temperature to yield 0.238 g of finepowder (87 turnovers/Ni). DSC (25 to 350° C., 15° C./min, second heat):Tm(onset)=170° C., Tm (end)=265° C., Heat of fusion=18 J/g.

Example 321

[1269] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g,10,000 equivalents/Ni) and anhydrous methylene chloride (48.5 ml) wereadded. A solution of EtAlCl₂ was added while stirring (2.92 ml, 1.0 M intoluene, 200 equivalents/Ni). After stirring for 163 hours, the solutionwas filtered and the solids were washed several times on the filter withpentane. The polymer was dried in vacuo for 12 hours at room temperatureto yield 1.64 g of fine powder (1640 turnovers/Ni). A DSC thermalfractionation experiment was done according to the procedure of Example312. A DSC was then recorded from 0° C. to 330° C. at 10° C./min. Tg=92°C., Tm (onset)=150° C., Tm (end)=250° C., Heat of fusion=11.4 J/g.

Example 322

[1270] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g,10,000 equivalents/Ni) was added. A solution of i-BuAlCl₂ was addedwhile stirring (2.92 ml, 1.0 M in toluene, 200 equivalents/Ni). Afterstirring for 163 hours, the solution was filtered and the solids werewashed several times on the filter with pentane. The polymer was driedin vacuo for 12 hours at room temperature to yield 1.99 g of fine powder(1990 turnovers/Ni). The polymer was pressed at 292° C. to give atransparent, light gray, tough film. A DSC thermal fractionationexperiment was done according to the procedure of Example 312. A DSC wasthen recorded from 0° C. to 330° C. at 10° C./min. Tg=103° C., Tm(onset)=150° C., Tm (end)=290° C., Heat of fusion=27 J/g.

Example 323

[1271] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed into a glassvial in the dry box (0.0932 g, 0.146 mmol). Cyclopentene (5.0 g, 500equivalents/Ni) and toluene (6.54 ml) were added. A solution of PMAO(Akzo Nobel Polymethylaluminoxane) was added while stirring (3.16 ml,2.32 M Al in toluene, 50 equivalents/Ni). After stirring for 163 hours,the solution was filtered and the solids were washed several times onthe filter with pentane. The polymer was dried in vacuo for 12 hours atroom temperature to yield 3.64 g of fine powder (364 turnovers/Ni). Thepolymer was pressed at 292° C. to give a brown film that seemed tough,but failed along a straight line when it broke. A DSC thermalfractionation experiment was done according to the procedure of Example312 was then recorded from 0° C. to 330° C. at 10° C./min. Tg=100° C.,Tm (onset)=150° C., Tm (end)=270° C., Heat of fusion=21 J/g.

Example 324

[1272] A mixture of 20 mg (0.032 mmol) of NiBr₂[(2,6-iPrPh)₂DABMe₂] wasmagnetically-stirred under nitrogen in a 50-mL Schlenk flask with 15 mLof dry, deaerated toluene as 0.6 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture became deep blue-black. Then 2.5 mL(14 mmol) of beta-citronellene, (CH₃)₂C═CHCH₂CH₂CH(CH₃)CH═CH₂, wasinjected and the mixture was immediately pressurized with ethylene at190 kPa (absolute) and was stirred at 23° C. for 17 h; by the end of 17h, the solution was too thick to stir. The ethylene was vented and thetoluene solution was stirred with 6N HCl and methanol and was decanted.The polymer was stirred with refluxing methanol for an hour to extractsolvent; oven-drying yielded 0.90 g of rubbery polyethylene. ¹H NMR(CDCl₃) showed a CH₂:CH₃ ratio of 83:12, which is 101 CH₃'s per 1000CH₂'s; there were small peaks for the beta-citronellene isopropylidenedimethyls (1.60 and 1.68 ppm), as well as a tiny peak for vinyl H (5.0ppm); diene incorporation was estimated at 0.7 mol %. Differentialscanning calorimetry: −51° C. (Tg). GPC data (trichlorobenzene, 135° C.;PE standard): Mn=23,200; Mw=79,200; Mz=154,000; Mw/Mn=3.42.

Example 325

[1273] A 15-mg (0.024-mmol) sample of NiBr₂[(2,6-i-PrPh)₂DABMe2] wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene and 5 mL (27 mmol) of dry, deaerated1,9-decadiene. Then 0.6 mL of polymethylalumoxane (1.7M MAO in heptane;contains about 30% isobutyl groups) was injected; the tan suspension didnot change color. The mixture was pressurized with ethylene to 190 kPa(absolute) and was stirred for 1 hr; it began to grow green-gray anddarker in color, so 0.6 mL more MAO was added, after which the mixturesoon turned deep greenblack. The reaction was stirred for 16 hr and theethylene was then vented; by this time the solution had become thick andunstirrable. The mixture was stirred with refluxing 6N HCl and methanol,and the polymer was washed with methanol, pressed free of solvent, anddried under high vacuum to yield 1.0 g of rubbery polyethylene. Thepolymer was insoluble in hot dichlorobenzene, demonstratingincorporation of the diene.

Example 326

[1274] A 21-mg (0.034-mmol) sample of NiBr₂[(2,6-i-PrPh)₂DABMe₂] wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of 2.9M polymethylalumoxane wasinjected; the red-brown suspension became deep green. The mixture waspurged with ethylene and then 2.0 mL (1.4 g; 15 mmol) of2-methyl-1,5-hexadiene was added; the mixture was pressurized withethylene to 190 kPa and was stirred for 18 h; the solution became brown.The ethylene was vented and the toluene solution was stirred with 6N HCland methanol and was separated; rotary evaporation of the toluene layeryielded, after acetone washing to remove catalyst, 47 mg of viscousliquid polymer. ¹H NMR (CDCl₃) showed a CH₂:CH₃ ratio of 82:15, which is130 CH₃'s per 1000 CH₂'s. There were also peaks for the incorporateddiene at 1.72 ppm (0.5H; CH ₃—C═CH₂) and 4.68 ppm (0.3H; CH₃—C═CH ₂) andno evidence of terminal vinyl (—CH═CH₂; 4.95 and 5.80 ppm) fromunincorporated diene. The level of diene incorporation was about 0.7 mol%.

Example 327

[1275] A 30-mg (0.049-mmol) sample of NiBr₂[(2,6-i-PrPh)₂DABMe₂] wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 1.0 mL of methylalumoxane (1.7M inheptane; contains about 30% isobutyl groups) was injected; the red-brownsuspension became deep green. The mixture was saturated with ethyleneand then 0.5 mL (0.38 g; 3.0 mmol) of 2-methyl-2,7-octadiene was added;the mixture was pressurized with ethylene to 190 kPa (absolute) and wasstirred for 18 h; the solution became brown. The ethylene was vented andthe toluene solution was stirred with 6N HCl and methanol and wasseparated; rotary evaporation of the toluene yielded, after acetonewashing to remove catalyst, 0.15 g of viscous liquid polymer. ¹H NMR(CDCl₃) showed a CH₂:CH₃ ratio of 81.5:13.5, which is 117 CH₃'s per 1000CH₂'s. The level of diene incorporation was about 0.5-1.0 mol %, judgingfrom the diene isopropylidene methyls at 1.60 and 1.69 ppm.

Examples 328-335

[1276] Acrylate Chelate Complexes. The chelate complexes for theseexamples were generated in situ for NMR studies by the reaction of[(ArN═C(R)—C(R)═NAr)Pdme(OEt₂)]BAF with H₂C═CHC(O)OR′ and on apreparative scale by the reaction of NaBAF with(ArN═C(R)—C(R)═NAr)PdMeCl and H₂C═CHC(O)OR′ (vide infra). In theseexamples, the following labeling scheme is used to identify thedifferent chelate complexes that were observed and/or isolated.Assignments of all ¹H NMR chelate resonances were confirmed byhomonuclear decoupling experiments.

General Procedure for the Synthesis of Chelate Complexes

[1277] A gastight microliter syringe was used to add 1.1 equiv ofH₂C═CHC(O)OR′ to a mixture of 1 equiv of NaBAF and 1 equiv of[(2,6-i-PrPh)₂DABR₂)PdMeCl suspended in 25 mL of Et₂O. The sides of theSchlenk flask were rinsed with an additional 25 mL of Et₂O and thefreaction mixture was stirred for 1-2 days at RT. Sodium chloride wasremoved from the reaction mixture via filtration, yielding a clearorange solution. The Et₂O was removed in vacuo and the product waswashed with hexane and dried in vacuo. For R′=Me or t-Bu, no furtherpurification was necessary (yields >87%). Recrystallization lowered theyield of product and did not result in separation of the isomericmixtures.

[1278] For R′═—CH₂(CF₂)₆CF₃, contamination of the product with unreactedNaBAF was sometimes observed. Filtration of a CH₂Cl₂ solution of theproduct removed the NaBAF. The CH₂Cl₂ was then removed in vacuo to yielda partially oily product. A brittle foam was obtained by dissolving theproduct in Et₂O and removing the Et₂O in vacuo (yields >59%). Althoughisolable, chelate complexes derived from FOA tended to be less stablethan those derived from MA or t-BuA and decomposed with time oradditional handling.

Spectral Data for the BAF Counterion

[1279] The following ¹H and ¹³C spectroscopic assignments of the BAFcounterion in CD₂Cl₂ were invariant for different complexes andtemperatures and are not repeated in the spectroscopic data for each ofthe cationic complexes: (BAF). ¹H NMR (CD₂Cl₂) δ7.74 (s, 8, H_(o)), 7.57(s, 4, H_(p)); ¹³C NMR (CD₂Cl₂) δ162.2 (q, J_(CB)=37.4, C_(ipso)), 135.2(C_(o)), 129.3 (q, J_(CF)=31.3, C_(m)), 125.0 (q, J_(CF)=272.5, CF₃),117.9 (C_(p)).

Example 328

[1280] The above synthesis using [(2,6-i-PrPh)₂DABH₂]PdMeCl (937 mg,1.76 mmol), NaBAF (1.56 g, 1.75 mmol), and MA (175 μL, 1.1 equiv) wasfollowed and the reaction mixture was stirred for 12 h. The resultingorange powder (2.44 g, 96.0%) consisted of a mixture of 6a(Me) (91%),5′a(Me) (5%), and 5a(Me) (4%), according to ¹H NMR spectroscopy. 6a(Me):¹H NMR (CD₂Cl₂, 400 MHz, rt) δ8.31 and 8.26 (s, 1 each, N═C(H)—C′(H)═N),7.5-7.2 (m, 6, H_(aryl)), 3.17 (s, 3, OMe), 3.14 and 3.11 (septet, 2each, CHMe₂ and C′HMe₂), 2.48 (t, 2, J=5.8, CH₂C(O)), 1.75 (t, 2, J=5.8,PdCH₂), 1.38, 1.32, 1.25 and 1.22 (d, 6 each, J=6.8, CHMeMe′ andC′HMeMe′), 0.73 (pentet, 2, J=5.8, PdCH₂CH₂CH₂C(O)); ¹³C NMR (CD₂Cl₂,100 MHz, rt) δ183.9 (C(O)), 167.1 (J_(CH)=181.4, N═C(H)), 160.7(J_(CH)=181.3, N═C′(H)), 142.9 and 142.4 (Ar, Ar′: C_(ipso)), 139.7 and138.7 (Ar, Ar′: C_(ipso)), 129.8 and 129.0 (Ar, Ar′: C_(p)), 124.6 and124.1 (Ar, Ar′: C_(m)), 55.2 (OMe), 35.9 and 32.3 (PdCH₂CH₂CH₂C(O)),29.3 and 29.1 (CHMe₂, C′HMe₂), 23.8 (PdCH₂CH₂CH₂C(O)), 24.5, 23.9, 23.2and 22.5 (CHMeMe′, C′HMeMe′); IR (CH₂Cl₂) 1640 cm⁻¹ [ν(C(O))]. 5′(H,Me):¹³C NMR (CD₂Cl₂, 100 MHz, rt) δ193.2 (C(O)). Anal. Calcd for (C₆₃H₅₇BF₂₄N₂O₂Pd): C, 52.28; H, 3.97; N, 1.94. Found: C, 52.08; H, 3.75; N, 1.61.

Example 329

[1281] The above synthesis using [(2,6-i-PrPh)₂DABMe₂]PdMeCl (634 mg,1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 μL, 1.1 equiv) wasfollowed. The reaction mixture was stirred for 2 days and the productwas recrystallized from CH₂Cl₂ at −30° C. to give 956 mg of orangecrystals (57.3%, 2 crops). The crystals consisted of a mixture of 6b(Me)(87%), 5′b(Me) (11.5%), and 5b(Me) (1.5%), according to ¹H NMRspectroscopy. 6b(Me): ¹H NMR (CD₂Cl₂, 400 MHz, rt) δ7.43-7.26 (m, 6,H_(aryl)), 3.03 (s, 3, OMe), 2.95 (septet, 2, J=6.79, CHMe₂), 2.93(septet, 2, J=6.83, C″HMe₂), 2.39 (t, 2, J=5.86, CH₂C(O)), 2.22 and 2.20(N═C(Me)—C′(Me)═N), 1.41 (t, 2, J=5.74, PdCH₂), 1.37, 1.30, 1.25 and1.21 (s, 6 each, J=6.80-6.94, CHMeMe′, C′HMeMe′), 0.66 (pentet, 2,J=5.76, PdCH₂CH₂CH₂C(O)); ¹³C NMR (CD₂Cl₂, 100 MHz, rt) δ183.4 (C(O)),178.7 and 171.6 (N═C—C′═N), 140.8 and 140.5 (Ar, Ar′: C_(ipso)), 138.6and 138.0 (Ar, Ar′: C_(o)), 129.3 and 128.3 (Ar, Ar′: C_(p)), 124.9 and124.4 (Ar, Ar′: C_(m)), 54.9 (OMe), 35.8 and 30.3 (PdCH₂CH₂CH₂C(O)),29.5 and 29.2 (CHMe₂, C′HMe₂), 23.7 (PdCH₂CH₂CH₂C(O)), 23.91, 23.86,23.20 and 23.14 (CHMeMe′, C′HMeMe′), 21.6 and 19.9 (N═C(Me)—C′(Me)═N);IR (CH₂Cl₂) 1643 cm⁻¹ [ν(C(O))]. 5′b(Me): ¹H NMR (CD₂Cl₂, 400 MHz, rt)δ3.47 (s, 3, OMe), 2.54 (m, 1, CHMeC(O)), 2.19 and 2.18 (s, 3 each,N═C(Me)—C′(Me)═N), 1.02 (d, 3, J=7.23, CHMeC(O)); ¹³C NMR (CD₂Cl₂, 100MHz, rt) δ194.5 (C(O)), 179.2 and 172.2 (N═C—C′═N), 55.6 (OMe), 44.3(CHMeC(O)), 28.4 (PdCH₂), 21.2 and 19.6 (N═C(Me)—C′(Me)═N), 18.1(CHMeC(O)). 5b(Me): ¹H NMR (CD₂Cl₂, 400 MHz, rt) δ0.26 (d, 3, PdCHMe).Anal. Calcd for (C₆₅H₆₁BF₂₄N₂O₂Pd): C, 52.92; H, 4.17; N, 1.90. Found:C, 52.91; H, 4.09; N, 1.68.

Example 330

[1282] The above synthesis was followed using [(2,6-i-PrPh)₂DABAn]PdMeCl(744 mg, 1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 μL, 1.1equiv). The reaction mixture was stirred for 2 days and the product wasrecrystallized from CH₂Cl₂ at −30° C. to give 600 mg (33.8%, 2 crops) ofa mixture of 6c(Me) (85%), 5′c(Me) (8%), 5″c(Me) (6%), and 5c(Me) (1%),according to ¹H NMR spectroscopy. 6c(Me): ¹H NMR (CD₂Cl₂) 400 MHz, rt)δ8.17 (d, 1, J=8.37, An: H_(p)), 8.15 (d, 1, J=3.49, An′: H′_(p)),7.62-7.40 (m, 8, An, An′: H_(m), H′_(m); Ar: H_(m), H_(p); Ar′: H′_(m),H′_(p)), 7.08 (d, 1, J=7.19, An: H_(o)), 6.60 (d, 1, J=7.44, An′:H′_(o)), 3.37 (septet, 2, J=6.79, CHMe₂), 3.33 (septet, 2, J=6.86,C′HMe₂), 2.55 (t, 2, J=5.93, CH₂C(O)), 1.79 (t, 2, J=5.66, PdCH₂), 1.45,1.42, 1.13 and 1.02 (d, 6 each, J=6.79-6.90, CHMeMe′, C′HMeMe′), 0.80(pentet, 2, J=5.82, PdCH₂CH₂CH₂C(O)); ¹³C NMR (CD₂Cl₂, 100 MHz, rt)δ183.5 (C(O)), 175.3 and 168.7 (N═C—C′═N), 145.9 (An: quaternary C),141.3 and 140.5 (Ar, Ar′: C_(ipso)), 139.7 and 138.4 (Ar, Ar′: C_(o)),133.3 and 132.6 (An: CH), 131.9 (An: quaternary C), 129.8, 129.7, 129.6and 128.5 (Ar, Ar′: Cp; An: CH), 126.44 and 125.8 (An: quaternary C),126.4 and 125.6 (An: CH), 125.5 and 124.6 (Ar, Ar′: C_(m)), 55.0 (OMe),35.9 and 31.3 (PdCH₂CH₂CH₂C(O)), 29.7 and 29.4 (CHMe₂, C′HMe₂), 24.1(PdCH₂CH₂CH₂C(O)), 24.1, 23.8, 23.32 and 23.27 (CHMeMe′, C′HMeMe′); IR(CH₂Cl₂) 1644 cm⁻¹ [ν(C(O))]. 5′c(Me): ¹H NMR (CD₂Cl₂, 400 MHz, rt)δ3.64 (s, 3, OMe), 2.70 (m, 1, CHMeC(O)); ¹³C NMR (CD₂Cl₂, 100 MHz, rt)δ192.8 (C(O)). 5″c(Me): ¹H NMR (CD₂Cl₂, 400 MHz, rt) δ6 3.67 (s, 3,OMe), 2.46 (t, 2, J=6.99, CH₂C(O)), 1.72 (t, 2, J=7.04, PdCH₂). 5c(Me):¹H NMR (CD₂Cl₂, 400 MHz, rt) δ0.44 (d, 3, PdCHMe). Anal. Calcd for(C₇₃H₆₁BF₂ ₄N₂O₂Pd): C, 55.80; H, 3.91; N, 1.78. Found: C, 55.76; H,3.82; N, 1.62.

Example 331

[1283] The above synthesis was followed using [(2,6-i-PrPh)₂DABH₂]PdMeCl(509 mg, 0.954 mmol), NaBAF (845 mg, 0.953 mmol), and t-BuA (154 μL, 1.1equiv). The reaction mixture was stirred for 1 day and yielded an orangepowder (1.24 g, 87.3%) that was composed of a mixture of 6a(t-Bu) (50%),5′a(t-Bu) (42%), and 5a(t-Bu) (8%), according to ¹H NMR spectroscopy.6a(t-Bu): ¹H NMR (CD₂Cl₂, 400 MHz, rt) δ8.27 and 8.25 (N═C(H)—C′(H)═N),7.45-7.20 (m, 6, H_(aryl)), 3.20 and 3.11 (septet, 2 each, J=6.9, CHMe₂and C′HMe₂), 2.42 (t, 2, J=5.9, CH₂C(O)), 1.77 (t, 2, J=5.3, PdCH₂),1.39, 1.36, 1.22 and 1.21 (d, 6 each, J=6.7, CHMeMe′ and C′HMeMe′), 1.01(s, 9, OCMe₃), 0.68 (pentet, 2, J=6.1, PdCH₂CH₂CH₂C(O)); ¹³C NMR(CD₂Cl₂, 100 MHz, rt, excluding Ar resonances) δ182.6 (C(O)), 88.8(OCMe₃), 37.8, 33.6 and 23.9 (PdCH₂CH₂CH₂C(O)), 29.3 and 29.0 (CHMe₂,C′HMe₂), 27.8 (OCMe₃), 24.8, 24.5, 22.7 and 22.6 (CHMeMe′, C′HMeMe′); IR(CH₂Cl₂) 1615 cm⁻¹ [ν(C(O))]; 5′a(t-Bu): ¹H NMR (CD₂Cl₂, 400 MHz, rt;excluding Ar and i-Pr resonances) δ8.29 and 8.22 (s, 1 each,N═C(H)—C′(H)═N), 2.53 (q, 1, J=7.3, C(H)(Me)C(O)), 1.75 (d, 1, J=8.9,PdCHH′), 1.53 (dd, 1, J=9.0, 7.0, PdCHH′), 1.16 (OCMe₃); ¹³C NMR(CD₂Cl₂, 100 MHz, rt; excluding Ar resonances) δ194.0 (C(O)), 90.6(OCMe₃), 45.9 (CHMeC(O)), 30.0 (PdCH₂), 29.4, 29.3, 29.1 and 29.1(CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 27.7 (OCMe₃), 24.6, 24.4, 23.81,23.79, 23.3, 23.3, 22.62 and 22.58 (CHMeMe′, C′HMeMe′, C″HMeMe′,C′″HMeMe′), 18.7 (CHMeC(O)); IR (CH₂Cl₂) 1577 cm⁻¹ [ν(C(O))]. 5a(t-Bu):¹H NMR (vide infra); ¹³C NMR (CD₂Cl₂, 100 MHz, rt) δ190.4 (C(O)), 166.7and 160.7 (N═C—C′═N), 48.1 (CH₂C(O)), 35.3 (PdCHMe). Anal. Calcd for(C₆₆H₆₃BF₂₄N₂O₂Pd): C, 53.22; H, 4.26; N, 1.88. Found: C, 53.55; H,4.20; N, 1.59.

Example 332

[1284] The above synthesis using [(2,6-i-PrPh)₂DABMe₂]PdMeCl (499 mg,0.889 mmol), NaBAF (786 mg, 0.887 mmol), and t-BuA (145 μL, 1.1 equiv)was followed. The reaction mixture was stirred for 1 day to yield anorange powder (1.24 g, 91.8%) that consisted of a mixture of 6b(t-Bu)(26%), 5′b(t-Bu) (63%), and 5b(t-Bu) (11%), according to ¹H NMRspectroscopy. ¹H NMR (CD₂Cl₂, 300 MHz, rt; diagnostic resonances only)6b(t-Bu): δ2.35 (t, 2, J=6.1, CH₂C(O)), 0.97 (s, 9, OCMe₃), 0.60(pentet, 2, J=5.7, PdCH₂CH₂CH₂C(O)); 5′b(t-Bu): δ2.43 (q, 1, J=7.2,CHMeC(O)), 1.08 (s, 9, OCMe₃); 5b(t-Bu): δ0.99 (s, 9, OCMe₃), 0.29 (d,3, J=6.74, PdCHMe); ¹³C NMR (CD₂Cl₂, 75 MHz, rt; diagnostic resonancesonly) 6b(t-Bu): δ182.3 (C(O)), 88.3 (OCMe₃), 37.9 and 31.9(PdCH₂CH₂CH₂C(O)),. 27.9 (OCMe₃), 22.0 and 20.1 (N═C(Me)—C′(Me)═N);5′b(t-Bu): δ193.8 (C(O)), 178.8 and 171.8 (N═C—C′═N), 90.0 (OCMe₃), 45.8(CHMeC(O)), 28.7 (PdCH₂), 21.1 and 19.6 (N═C(Me)—C′(Me)═N), 18.6(CHMeC(O)); 5b(t-Bu) δ190.7 (C(O)), 48.4 (CH₂C(O)), 33.9 (PdCHMe). Anal.Calcd for (C₆₈H₆₇BF₂₄N₂O₂Pd): C, 53.82; H, 4.45; N, 1.85. Found: C,53.62; H, 4.32; N, 1.55.

Example 333

[1285] The above synthesis was followed using [(2,6-i-PrPh)₂DABAn]PdMeCl(503 mg, 0.765 mmol), NaBAF (687 mg, 0.765 mmol), and t-BuA (125 μL, 1.1equiv). The reaction mixture was stirred for 1 day to yield an orangepowder (1.08 g, 87.8%) that consisted of a mixture of 6c(t-Bu) (47%),5′c(t-Bu) (50%), and 5c(t-Bu) (3%), according to ¹H NMR spectroscopy. ¹HNMR (CD₂Cl₂, 300 MHz, rt; diagnostic chelate resonances only) 6c(t-Bu):δ2.48 (t, 2, J=6.05, CH₂C(O)), 1.80 (t, 2, PdCH₂), 1.07 (s, 9, OCMe₃),0.73 (pentet, 2, J=5.87, PdCH₂CH₂CH₂C(O)); 5′c(t-Bu): δ2.57 (q, 1,J=6.96, CHMeC(O)), 1.58 (dd, 1, J=8.80, 6.96, PdCHH′), 1.21 (s, 9,OCMe₃); 5c(t-Bu): δ0.73 (d, 3, PdCHMe); ¹³C NMR (CD₂Cl₂, 75 MHz, rt;diagnostic chelate resonances only) 6c(t-Bu): δ181.8 (C(O)), 87.9(OCMe₃), 37.4 and 32.2 (PdCH₂CH₂CH₂C(O)), 27.4 (OCMe₃); 5′c(t-Bu):δ193.0 (C(O)), 89.5 (OCMe₃), 45.5 (CHMeC(O)), 28.5 (PdCH₂), 27.2(OCMe₃), 18.1 (CHMeC(O)). Anal. Calcd for (C₇₆H₆₇BF₂₄N₂O₂Pd): C, 56.57;H, 4.19; N, 1.74. Found: C, 56.63; H, 4.06; N, 1.52.

Example 334

[1286] The above synthesis using [(2,6-i-PrPh)₂DABH₂]PdMeCl (601 mg,1.13 mmol), NaBAF (998 mg, 1.13 mmol), and FOA (337 μL, 1.1 equiv)yielded after 1 day of stirring 1.21 g (59.2%) of 6a(FOA) as a red foam:¹H NMR (CD₂Cl₂, 300 MHz, 0;C) δ8.33 and 8.27 (s, 1 each,N═C(H)—C′(H)═N), 7.4-7.2 (m, 6, H_(aryl)), 3.85 (t, 2, J_(HF)=13.05,OCH₂(CF₂)₆CF₃), 3.13 and 3.08 (septet, 2 each, J=6.9, CHMe₂ and C′HMe₂),2.65 (t, 2, J=5.62, CH₂C(O)), 1.74 (t, 2, J=5.59, PdCH₂), 1.36, 1.29,1.15 and 1.13 (d, 6 each, J=6.73-6.82, CHMeMe′, C′HMeMe′), 0.76 (pentet,2, J=5.44, PdCH₂CH₂CH₂C(O)).

Example 335

[1287] The above synthesis using [(2,6-i-PrPh)₂DABMe₂]PdMeCl (637 mg,1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and FOA (339 μL, 1.1 equiv)yielded after 1 day of stirring 1.36 g (65.2%) of 6b(FOA) as a yellowfoam: ¹H NMR (CD₂Cl_(2, 300) MHz, 0;C) δ7.5-7.0 (m, 6, H_(aryl)), 3.64(t, 2, J_(HF)=12.72, OCH₂(CF₂)₆CF₃), 2.90 and 2.88 (septet, 2, J=6.74,CHMe₂ and C′HMe₂), 2.56 (t, 2, J=5.82, CH₂C(O)), 2.32 and 2.22(N═C(Me)—C′(Me)═N), 1.34, 1.27, 1.23 and 1.19 (d, 6 each, J=6.75-6.82,CHMeMe′, C′HMeMe′), 0.68 (pentet, 2, J=5.83, PdCH₂CH₂CH₂C(O)).

Examples 336-338

[1288] The labeling scheme given in Examples 328-335 is also used here.Spectral data for the BAF counterion is the same as given in Examples328-335.

[1289] Low-Temperature NMR Observation of Methyl Acrylate Olefin ComplexFormation and Chelate Formation and Rearrangement. One equivalent of MAwas added to an NMR tube containing a 0.0198 M solution of{[(2,6-iPrPh)₂DABH₂]PdMe(OEt₂)]}BAF in CD₂Cl₂ (700 μL) at −78° C., andthe tube was transferred to the precooled NMR probe. After 14.25 min at−80° C., approximately 80% of the ether adduct had been converted to theolefin complex. Two sets of bound olefin resonances were observed in a86:14 ratio. This observation is consistent with the existence of twodifferent rotamers of the olefin complex. Insertion of MA into the Pd—Mebond occurred with predominantly 2,1 regiochemistry to give the4-membered chelate 4a(Me) at −80;C (t_(1/2)˜2.0 h). The resonances forthe major rotamer of the olefin complex disappeared before those of theminor rotamer. Much slower conversion of 4a(Me) to the 5-memberedchelate 5a(Me) also began at −80° C. Upon warming to −60° C., completeand selective formation of 5a(Me) occurred in less than 4 h. The5-membered chelate was relatively stable at temperatures below −50° C.,however, upon warming to −20° C., rearrangement to the 6-memberedchelate 6a(Me) was observed. NMR spectral data for the olefin complex,4a(Me), and 5a(Me) follow. Spectral data for 6a(Me) is identical to thatof the isolated chelate complex (see Examples 328-335).

Example 336

[1290] {[(2,6-i-PrPh)₂DABH₂]Pd(Me) [H₂C═CHC(O)OMe]}BAF.

[1291]¹H NMR (CD₂Cl₂, −80° C., 400 MHz) Major Rotamer: δ8.45 and 8.32(s, 1 each, N═C(H)—C′(H)═N), 7.5-7.1 (m, 6, H_(aryl)), 5.14 (d, J=15.2,HH′C═), 4.96 (dd, J=14.9, 8.6, ═CHC(O)), 4.63 (d, J=8.5, HH′C═), 3.68(s, 3, OMe), 3.03, 2.90, 2.80 and 2.67 (septet, 1 each, CHMe₂, C′HMe₂,C″HMe₂, C′″HMe₂), 1.5-1.0 (doublets, 24, CHMe₂), 0.61 (s, 3, PdMe);Minor Rotamer: δ8.25 and 8.18 (s, 1 each, N═C(H)—C′(H)═N), 5.25 (d, 1,HH′C═), 4.78 (dd, 1, ═CHC(O)), 4.58 (d, 1, HH′C═), 3.63 (OMe).

Example 337

[1292] {[(2,6-i-PrPh)₂DABH₂]Pd[CHEtC(O)OMe]}BAF 4a(Me).

[1293]¹H NMR (CD₂Cl₂, 400 MHz, −60° C.) δ8.25 and 8.22 (N═C(H)—C′(H)═N),7.5-7.2 (m, 6, H_(aryl)), 3.74 (s, 3, OMe), 3.55, 3.27, 3.08 and 2.76(m, 1 each, CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 2.62 (dd, J=10.8, 2.9,CHEt), 1.4-1.0 (doublets, 24, CHMe₂), 0.79 and −0.49 (m, 1 each,CH(CHH′Me)), 0.71 (t, 3, J=6.6, CH(CHH′Me)).

Example 338

[1294] {[(2,6-i-PrPh)₂DABH₂]Pd[CHMeCH₂C(O)OMe]}BAF 5a(Me). ¹H NMR(CD₂Cl₂, 400 MHz, −60;C) δ8.24 and 8.21 (N═C(H)—C′(H)═N), 7.4-7.2 (m, 6,H_(aryl)), 3.59 (s, 3, OMe), 3.47, 3.32, 2.98 and 2.81 (septet, 1 each,CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 3.08 (dd, 1, J=18.4, 7.3, CHH′C(O)),1.74 (pentet, 1, J=6.9, PdCHMe), 1.60 (d, 1, J=18.6, CHH′C(O)), 1.34 (d,6, J=5.6, C′HMeMe′ and C′″HMeMe′), 1.32 (d, 3, J=6.2, CHMeMe′), 1.24 (d,3, J=6.8, C″HMeMe′), 1.18 (d, 6, J=6.8, C′HMeMe′ and C″HMeMe′), 1.15 (d,3, J=6.8, C′″HMeMe′), 1.08 (d, 3, CHMeMe′), 0.35 (d, 3, J=6.9, PdCHMe);¹³C NMR (CD₂Cl₂, 100 MHz, −80° C.) δ190.5 (C(O)), 166.1 (J_(CH)═181,N═C(H)), 160.7 (J_(CH)═181, N═C′(H)), 142.8 and 141.6 (Ar, Ar′:C_(ipso)), 139.0, 138.6, 138.2 and 137.7 (Ar: C_(o), C_(o)′ and Ar′:C_(o), C_(o)′), 128.8 and 128.2 (Ar, Ar′: C_(p)), 124.1, 123.54, 123.48,123.4 (Ar: C_(m), C_(m)′ and Ar′: C_(m), C_(m)′), 55.5 (OMe), 45.1(CH₂C(O)), 35.6 (PdCHMe), 28.8, 28.5, 28.1 and 27.8 (CHMe₂, C′HMe₂,C″HMe₂, C′″HMe₂), 25.6, 24.2, 23.1, 23.0, 22.7, 22.3, 21.9, 21.3, and21.3 (CHMeMe′, C′HMeMe′, C″HMeMe′, C′″HMeMe′ and PdCHMe).

Example 339-342

[1295] The labeling scheme given in Examples 328-335 is also used forExamples 339-342. Spectral data for the BAF counterion is the same asgiven in Examples 328-335.

[1296] Low-Temperature NMR Observation of t-Butyl Acrylate OlefinComplex Formation and Chelate Formation and Rearrangement. One equiv oft-BuA was added to an NMR tube containing a 0.0323 M solution of{[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF in CD₂Cl₂ (700 μL) at −78° C., andthe tube was transferred to the precooled NMR probe. The olefin complexwas observed at −80° C., and the probe was then warmed to −70° C. After1 h at −70° C., conversion to 5a(t-Bu) and 5′a(t-Bu) was almostcomplete, with small amounts (<10%) of the olefin complex and 4a(t-Bu)still present. Conversion of 5a(t-Bu) to 6a(t-Bu) was followed at −10°C. (t_(1/2)˜1 h) When this experiment was repeated using 5 equiv oft-BuA, conversion to 5a, 5′a and 6a was observed at −80° C. Afterallowing the solution to stand at rt for 5 days, partial conversion tothe unsubstituted 5-membered chelate 5″a(t-Bu) was observed. Spectraldata for the olefin complex, 4a(t-Bu), 5a(t-Bu) and 5″a(t-Bu) follow.Spectral data for 5′a(t-Bu) and 6a(t-Bu) are identical to that of theisolated chelate complexes (see Examples 328-335).

Example 339

[1297] {[(2,6-i-PrPh)₂DABH₂]PdMe[H₂C═CHC(O)O-t-Bu]}BAF.

[1298]¹H NMR (CD₂Cl₂, 400 MHz, −80;C) δ8.45 and 8.30 (s, 1 eachN═C(H)—C′(H)═N), 7.4-7.2 (m, 6, H_(aryl)), 5.15 (d, 1, J=15.3, HH′C═),4.89 (dd, 1, J=14.7, 8.4, =CHC(O)), 4.61 (d, 1, J=7.7, HH′C═), 2.92,2.90, 2.80 and 2.64 (septets, 1 each, CHMe₂, C′HMe₂), C″HMe₂ andC′″HMe₂), 1.31 (s, 9, OCMe₃), 1.5-0.8 (doublets, 24, CHMe₂), 0.60 (s, 3,PdMe).

Example 340

[1299] {[(2,6-i-PrPh)₂DABH₂]Pd[CHEtC(O)O-t-Bu]}BAF 4a(t-Bu). ¹H NMR(CD₂Cl₂, 400 MHz, −70° C.) δ8.22 and 8.21 (s, 1 each, N═C(H)—C′(H)═N),2.21 (d, 1, J=9.2, PdCHEt), 0.71 (t, 3, J=7.9, PdCH(CH₂Me)), 0.5 and−0.4 (br m, 1 each, PdCH(CHH′Me)).

Example 341

[1300] {[(2,6-i-PrPh)₂DABH₂]Pd[CHMeCH₂C(O)O-t-Bu]}BAF 5a(t-Bu). ¹H NMR(CD₂Cl₂, 400 MHz, −40° C.) δ8.28 and 8.24 (s, 1 each, N═C(H)—C′(H)═N),7.4-7.2 (m, 6, H_(aryl)), 3.44, 3.32, 2.96 and 2.86 (septet, 1 each,CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 2.94 (dd, 1, J=18.6, 7.1, CHH′C(O)),1.79 (pentet, 1, J=6.7, PdCHMe), 1.62 (d, 1, J=18.5, CHH′C(O)), 1.4-1.0(doublets, 24, CHMe₂), 1.10 (s, 9, OCMe₃), 0.22 (d, 3, J=6.9, PdCHMe).

Example 342

[1301] {[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂C(O)O-t-Bu]}BAF 5″a(t-Bu). ¹H NMR(CD₂Cl₂, 400 MHz, rt) δ2.40 (t, 2, J=7.0, CH₂C(O)), 1.65 (t, 2, J=7.0,PdCH₂).

Example 343

[1302] The labeling scheme given in Examples 328-335 is also used forExample 343. Spectral data for the BAF counterion is the same as givenin Examples 328-335.

[1303] Low-Temperature NMR Observation of FOA Chelate Formation andRearrangement. One equiv of FOA was added to an NMR tube containing a0.0285 M solution of {[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF (1a) at −78;Cin CD₂Cl₂ (700 μL), and the tube was briefly shaken at this temperature.A ¹H NMR spectrum at −80° C. showed that FOA was not dissolved. Thesample was allowed to warm slightly as it was shaken again and anotherspectrum was then acquired at −80° C. Approximately equal amounts of5a(FOA) and 6a(FOA) were observed along with small amounts of the etheradduct 1a and FOA (an olefin complex was not observed). Rearrangement of5a(FOA) to 6a(FOA) was observed at −40° C. and was complete upon warmingto −30° C. NMR spectral data for 5a(FOA) follow. Spectral data for6a(FOA) are identical with that of the isolated complex (vide supra).

[1304] {[(2,6-i-PrPh)₂DABH₂]Pd[CHMeCH₂C(O)OCH₂ (CF₂)₆CF₃]}BAF 5a(FOA).

[1305]¹H NMR (CD₂Cl₂, 300 MHz, −40;C) δ8.23 and 8.22 (s, 1 each,N═C(H)—C′(H)═N), 3.47 (t, 2, J_(HF)=13.38, OCH₂(CF₂)₆CF₃), 3.20 (dd, 1,J=19.25, 7.28, CHH′C(O)), 2.58 (pentet, 1, J=6.99, PdCHMe), 1.77 (d, 1,J=19.81, CHH′C(O)), 0.33 (d, 3, J=6.88, PdCHMe). Spectral data for theBAF counterion is the same as given in Examples 328-335.

Example 344

[1306] NMR Observation of {[(2,6-i-PrPh)₂DABH₂]Pd[CHR″CH₂CH₂C(O)OMe]}BAFand {[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂C(O)OMe]}BAF. A solution of{[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF (21.5 mg, 0.0150 mmol) in 700 μL ofCD₂Cl₂ was prepared at −78° C. Ethylene (5 equiv) was added via gastightsyringe and the tube was shaken briefly to dissolve the ethylene. Methylacrylate (5 equiv) was then added to the solution, also via gastightmicroliter syringe, and the tube was shaken briefly again. The tube wastransferred to the NMR probe, which was precooled to −80° C. Resonancesconsistent with the formation of the ethylene adduct{[(2,6-i-PrPh)₂DABH₂]PdMe(H₂C═CH₂)}BAF were observed. The solution waswarmed and ethylene insertion was monitored at −40 to −20° C. Theconsumption of one equiv of methyl acrylate occurred as the last equivof ethylene disappeared, and resonances consistent with the formation ofa substituted 6-membered chelate complex{[(2,6-i-PrPh)₂DAH₂]Pd[CHR″CH₂CH₂C(O)OMe]}BAF were observed [8.30 and8.29 (N═C(H)—C′ (H)═N), 3.17 (OMe)]. The large upfield shift of themethoxy resonance is particularly diagnostic for formation of the6-membered chelate complex in these systems. The substituted 6-memberedchelate complex was observed at −20° C. and initially upon warming toRT. After 2 h at RT, decomposition of the substituted 6-membered chelatecomplex had begun. After 24 h at RT, an additional 0.5 equiv of MA hadbeen consumed and triplets at 2.42 and 1.66 ppm, consistent with theformation of the unsubstituted 5-membered chelate complex{[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂C(O)OMe]}BAF, were observed. Spectral datafor the BAF counterion is the same as given in Examples 328-335.

Example 345

[1307] NMR Observation of{[(2,6-i-PrPh)₂DABMe₂]Pd(CHR″CH₂CH₂C(O)OMe]}BAF. The procedure ofExample 344 was followed with analogous results, e.g., resonances forthe formation of a substituted 6-membered chelate complex{[(2,6-i-PrPh)₂DABMe₂]Pd [CHR″CH₂CH₂C(O)OMe]}BAF were observed followingcomplete ethylene consumption [3.03 (s, OMe), 3.12, 2.96, 2.89, 2.83(septets, CHMe₂, C′HMe₂, C″HMe₂ and C′″HMe₂), 2.23 and 2.19 (s,N═C(Me)—C′(Me)═N)]. Again, the large upfield shift of the methoxyresonance is diagnostic for the formation of the six-membered chelatecomplex. The observation of four i-propyl methine resonances (vs. twoi-propyl methine resonances in the unsubstituted six-membered chelatecomplex) reflects the asymmetry introduced in the molecule due to theintroduction of the R″ substituent on C_(α) of the chelate ring andfurther supports the proposed structure. Spectral data for the BAFcounterion is the same as given in Examples 328-335.

Example 346

[1308] {[(2,6-i-PrPh)₂DABH₂]Pd(H₂C═CH₂) [CH₂CH₂CH₂C(O)OMe]}BAF. Ethylenewas transferred at −78° C. via gastight microliter syringe to an NMRtube containing a CD₂Cl₂ solution of the chelate complex{[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂CH₂C(O)OMe]}BAF. NMR data for the ethylenecomplex follow; it was observed in equilibrium with the starting chelatecomplex: ¹HÊNMR (CD₂Cl₂, 300 MHz, 182°K.) δ8.30 and 8.29 (s, 1 each,N═C(H)—C′(H)═N), 7.38-7.24 (m, 6, H_(aryl)), 3.72 (s, 3, OMe), 3.43 (brs, 4, H₂C═CH₂), 3.10 (m, 2, CHMe₂), 2.70 (m, 2, C″HMe₂), 2.20 (m, 2,CH₂C(O)), 1.25, 1.16, 1.09 and 1.07 (d, 6 each, J=7, CHMeMe′, C′HMeMe′),1.20 (PdCH₂ (obscured by CHMeMe′ peaks, observed by H,H-COSY)), 0.56 (m,2, PdCH₂CH₂CH₂C(O)); ¹³C NMR (CD₂Cl₂, 400 MHz, −80° C.) δ178.9 (C(O)),162.7 (J_(CH)=179, N═C), 162.5 (J_(CH)=179, N═C′), 141.3 and 140.5 (Ar,Ar′: C_(ipso)), 138.5 and 138.1 (Ar, Ar′: C_(o)), 128.5 and 128.3 (Ar,Ar′: C_(p)), 124.1 and 124.0 (Ar, Ar′: C_(o)), 122.9 (J_(CH)=159.3, freeH₂C═CH₂), 70.2 (J_(CH)=158.6, bound H₂C═CH₂), 53.0 (OMe), 36.5, 33.0 and22.6 (PdCH₂CH₂CH₂C(O)), 27.8 (CHMe₂, C′HMe₂), 25.6, 25.3, 22.1 and 21.4(CHMeMe′, C′HMeMe′). Spectral data for the BAF counterion is the same asgiven in Examples 328-335.

Example 347

[1309] {[(2,6-i-PrPh)₂DABMe₂]Pd(H₂C═CH₂) [(CH₂CH₂CH₂C(O)OMe]}BAF.Ethylene was transferred at −78° C. via gastight microliter syringe toan NMR tube containing a CD₂Cl₂ solution of the chelate complex{[(2,6-i-PrPh)₂DABMe₂]Pd[CH₂CH₂CH₂C(O)OMe]}BAF. NMR data for theethylene complex follow; even at low temperature and in the presence ofa large excess of ethylene, this complex could only be observed in thepresence of at least an equimolar amount of the correspondingsix-membered chelate: ¹HÊNMR (CD₂Cl₂, 300 MHz, 172° K.): δ7.35-7.19 (m,6, H_(aryl)), 4.31 (br s, 4, H₂C═CH₂), 3.45 (s, 3, OMe), 2.73-2.54 (m,4, CHMe₂), 2.38 and 2.22 (s, 3 each, N═C(Me)—C′(Me)═N), 1.64 (m, 2,CH₂C(O)), 1.02 (d, 6, J=6, CHMeMe″). From the available H,H-COSY data,the remaining PdCH₂CH₂CH₂C(O)— and CHMe-signals could not beunambiguously assigned, due to the presence of the six-membered chelate.Spectral data for the BAF counterion is the same as given in Examples328-335.

Example 348

[1310] {[(2,6-i-PrPh)₂DABAn]Pd(H₂C═CH₂) [CH₂CH₂CH₂C(O)OMe]}BAF. Ethylenewas transferred at −78° C. via gastight microliter syringe to an NMRtube containing a CD₂Cl₂ solution of the chelate complex{[(2,6-i-PrPh)₂DABAn]Pd(CH₂CH₂CH₂C(O)OMe)]BAF. NMR data for the ethylenecomplex follow; it was observed in equilibrium with the starting chelatecomplex: ¹H NMR (CD₂Cl₂, 300 MHz, 178° K.): δ8.06 and 8.02 (d, J=8, 1each, An and An′: H_(p) and H′_(p)), 7.50-7.38 (m, 8, An and An′: H′_(m)and H_(m), Ar: H_(m) and H_(p)), 6.48 (d, J=7, 2 , An and An′: H_(o) andH′_(o)), 4.56 (br s, 4, H₂C═CH₂), 3.45 (s, 3, OMe), 2.99 and 2.91 (m, 2each, CHMe₂ and C′HMe₂), 1.77 (m, 2, CH₂C(O)), 1.29, 1.27, 0.82 and 0.77(d, J=6-7, 6 each, CHMeMe′, C′HMeMe′). H,H-COSY reveals that theremaining PdCH₂CH₂CH₂C(O)-signals are obscured by the CHMe-signals at1.2 ppm. Spectral data for the BAF counterion is the same as given inExamples 328-335.

Example 349

[1311] {[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂CH₂C(O)OCH₂(CF₂)₆CF₃] (H₂C═CH₂)}BAF. Ethylene (0.78 equiv) was added via gastight microliter syringe toa 0.0105 M solution of the chelate complex{[(2,6-i-PrPh)₂DABH₂]Pd[CH₂CH₂CH₂C(O)OCH₂(CF₂)₆CF₃]}BAF in CD₂Cl₂ (700μL). NMR data for the ethylene complex follow; it was observed inequilibrium with the starting chelate complex: ¹H NMR (CD₂Cl₂, 300 MHz,213.0° K.) δ8.40 and 8.25 (N═C(H)—C′(H)═N), 7.5-7.1 (m, 6, H_(aryl)),4.50 (t, 2, J_(HF)=13.39, OCH₂(CF₂)₆CF₃), 4.41 (s, 4, H₂C═CH₂), 2.94 and2.70 (septet, 2 each, CHMe₂, C′HMe₂), 1.80 (t, 3, CH₂C(O)), 1.4-1.0(CHMeMe′, C′HMeMe′, PdCH₂CH₂CH₂C(O)). Spectral data for the BAFcounterion is the same as given in Examples 328-335.

Example 350

[1312] A 12 mg (0.02 mmol) sample of [(2,6-i-PrPh)₂DABAn]NiBr₂ wasplaced in a 25 mL high pressure cell. The reactor was purged with argon.The reactor was cooled to 0° C. before 2 mL of a 10% MAO solution intoluene was added under a positive argon purge. The reactor was filled(¾ full) with liquid CO₂ (4.5 MPa) and a 689 kPa head pressure ofethylene was added by continuous flow. A 6 degree exotherm was observed.A layer of polyethylene formed immediately at the ethylene CO₂interface. After 20 minutes, the cell was vented and the polyethyleneremoved from the reactor. The polymer was dried in vacuo for severalhours. Polyethylene (2.05 g) was isolated; M_(n)=597,000,M_(w)/M_(n)=2.29, T_(m)=128° C. This example demonstrates theapplicability of liquid CO₂ as a solvent for polymerization in thesecatalyst systems.

Example 351

[1313] A 12 mg (0.02 mmol) sample of [(2,6-i-PrPh)₂DABAn]NiBr₂ wasplaced in a 25 mL high pressure cell and the reactor was purged withargon. The reactor was heated to 40° C. and 2 mL of a 10% MAO solutionin toluene was added. CO₂ (20.7 MPa) and ethylene (3.5 MPa, continuousflow) was then added to the reactor. Polyethylene began adhering to thesapphire window within minutes. After 20 minutes, the cell was ventedand the polyethylene removed from the reactor. The polymer was dried invacuo for several hours. Polyethylene (0.95 g) was isolated;M_(n)=249,000, M_(w)/M_(n)=2.69, T_(m)=113° C. This example demonstratesthe applicability of supercritical CO₂ as a solvent for polymerizationin these catalyst systems.

Example 352

[1314] A standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂ was prepared asfollows: 1,2-difluorobenzene (10 mL) was added to 6.0 mg of[(2,6-i-PrPh)₂ DABAn]NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask.The standard solution was transferred to a Kontes flask and stored underan argon atmosphere.

[1315] A 1000 mL Parr® stirred autoclave under an argon atmosphere, wascharged with 1 mL of a standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂(8.3×10⁻⁷ mol), and 200 mL of dry, deaerated toluene. The reactor waspurged with ethylene before addition of 2 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 1.4 MPaas the internal temperature increased from 25° C. to 45° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to 30° C. After 10 minutes, the ethylene was vented andacetone and water were added to quench the reaction. Solid polyethylenewas recovered from the reactor collected and washed with 6 M HCl, H₂₀,and acetone. The resulting polymer was dried under high vacuum overnightto yield 7.0 g (1.8×10⁶ TO/h) of polyethylene. Differential scanningcalorimetry: T_(m)=118° C. (133 J/g). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=470,000;M_(w)=1,008,000; M_(w)/M_(n)=2.14. ¹³C-NMR analysis: total methyls/1000CH₂ (27.6), methyl (21.7), ethyl (2.6), propyl (0.7), butyl (1), amyl(0.4).

Example 353

[1316] A 1000 mL Parr® stirred autoclave under an argon atmosphere, wascharged with 1 mL of a standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂(8.3×10⁻⁷ mol), and 200 mL of dry, deaerated toluene. The reactor waspurged with ethylene before addition of 2 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 2.8 MPaas the internal temperature increased from 25° C. to 48° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 minutes, the ethylene was vented andacetone and water were added to quench the reaction. Solid polyethylenewas recovered from the reactor collected and washed with 6 M HCl, H₂O,and acetone. The resulting polymer was dried under high vacuum overnightto yield 8.85 g (2.3×10⁶ TO/h) of polyethylene. DSC: T_(m)=122° C. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=485,000;M_(w)=1,042,000; M_(w)/M_(n)=2.15. ¹³C-NMR analysis: total methyls/1000CH₂ (21.3), methyl (16.3), ethyl (2.1), propyl (0.7), butyl (0.9), amyl(0.2).

Example 354

[1317] A 1000 mL Parr® stirred autoclave under an argon atmosphere, wascharged with 1 mL of a standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂(8.3×10⁻⁷ mol), and 200 mL of dry, deaerated toluene. The reactor waspurged with ethylene before addition of 2 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 4.1 MPaas the internal temperature increased from 25° C. to 45° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6 M HCl, H₂O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 7.45 g (1.9×10⁶ TO/h) of polyethylene. DSC: T_(m)=126° C. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=510,000;M_(w)=1,109,000; M_(w)/M_(n)=2.17. ¹³C-NMR analysis: total methyls/1000CH₂ (5.1), methyl (5.1), ethyl (0), propyl (0), butyl (0), amyl (0).

Example 355

[1318] A 1 mg (1.7×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABH₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under argon. The autoclavewas sealed and 200 mL of dry toluene was added. The reactor was purgedwith ethylene before addition of 1.5 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 1.4 MPaas the internal temperature increased from 25° C. to 45° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6 M HCl, H₂O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 14.1 g (1.8×10⁶ TO/h) of polyethylene. DSC: T_(m)=126° C. (151J/g). GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as polyethylene using universal calibration theory):M_(n)=32,000; M_(w)=89,000; M_(w)/M_(n)=2.75.

Example 356

[1319] A 1 mg (1.7×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABH₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under argon. The autoclavewas sealed and 200 mL of dry toluene was added. The reactor was purgedwith ethylene before addition of 1.5 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 2.1 MPaas the internal temperature increased from 25° C. to 50° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6 M HCl, H₂O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 16.1 g (2×10⁶ TO/h) of polyethylene. DSC: T_(m)=129° C. (175 J/g).GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as polyethylene using universal calibration theory):M_(n)=40,000; M_(w)=89,000; M_(w)/M_(n)=2.22.

Example 357

[1320] A 1.2 mg (1.9×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under argon. The autoclavewas sealed and 200 mL of dry toluene was added. The reactor was purgedwith ethylene before addition of 2.0 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 1.4 MPaas the internal temperature increased from 24° C. to 31° C. withinseconds. Activation of the internal cooling system returned the reactortemperature to ˜25° C. After 12 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6 M HCl, H₂O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 8 g (9×10⁵ TO/h) of polyethylene. DSC: Broad melt beginningapproximately 0° C. with a maximum at 81° C. (25 J/g). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n)=468,000;M_(w)=1,300,000; M_(w)/M_(n)=2.81. ¹³C-NMR analysis: total methyls/1000CH₂ (46.6), methyl (37.0), ethyl (2.4), propyl (1.6), butyl (1.3), amyl(1.4).

Example 358

[1321] A 1.2 mg (1.9×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under argon. The autoclavewas sealed and 200 mL of dry toluene was added. The reactor was purgedwith ethylene before addition of 2.0 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 2.8 MPaas the internal temperature increased from 24° C. to 34° C. withinseconds. After 12 min, the ethylene was vented and acetone and waterwere added to quench the reaction. Solid polyethylene was recovered fromthe reactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 6.5 g(6×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately60° C. with a maximum at 109° C. (80 J/g). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=616,000; M_(w)=1,500,000;M_(w)/M_(n)=2.52. ¹³C-NMR analysis: total methyls/1000 CH₂ (32.0),methyl (24.6), ethyl (2.6), propyl (1.3), butyl (0.6), amyl (1.3).

Example 359

[1322] A 1.2 mg (1.9×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under argon. The autoclavewas sealed and 200 mL of dry toluene was added. The reactor was purgedwith ethylene before addition of 2.0 mL of a 10% MAO solution intoluene. The autoclave was rapidly pressurized with ethylene to 4.1 MPa.After 12 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 7.2 g(7×10⁵ TO/h) of polyethylene. GPC (trichlorobenzene, 135;C, polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=800,000; M_(w)=1,900,000; M_(w)/M_(n)=2.43.¹³C-NMR analysis: total methyls/1000 CH₂ (18.7), methyl (14.9), ethyl(1.7), propyl (1.1), butyl (0.3), amyl (0.4).

Example 360

[1323] A 1.5 mg (2.4×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ and200 mL of dry toluene was added to a Parr® 1000 mL stirred autoclaveunder an argon atmosphere. The reactor was heated to 50° C. and purgedwith ethylene before addition of 3.0 mL of a 7% MMAO solution inheptane. The autoclave was rapidly pressurized with ethylene to 690 kPa.After 10 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 6.25 g(6×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately−25° C. with a maximum at 50° C.; T_(g)=−36° C. GPC (trichlorobenzene,135;C, polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=260,000; M_(w)=736,000;M_(w)/M_(n)=2.83.

Example 361

[1324] A 1.5 mg (2.4×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ and200 mL of dry toluene was added to a Parr® 1000 mL stirred autoclaveunder an argon atmosphere. The reactor was heated to 65° C. and purgedwith ethylene before addition of 3.0 mL of a 7% MMAO solution inheptane. The autoclave was rapidly pressurized with ethylene to 690 kPa.After 10 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 7.6 g(7×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately−50° C. with a maximum at 24° C. GPC (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=176,000; M_(w)=438,000;M_(w)/M_(n)=2.49.

Example 362

[1325] A 1.5 mg (2.4×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ and200 mL of dry toluene was added to a Parr® 1000 mL stirred autoclaveunder an argon atmosphere. The reactor was heated to 80° C. and purgedwith ethylene before addition of 3.0 mL of a 7% MMAO solution inheptane. The autoclave was rapidly pressurized with ethylene to 690 kPa.After 10 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 1.0 g(0.9×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately−50° C. with a maximum at −12° C. GPC (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=153,000; M_(w)=273,000;M_(w)/M_(n)=1.79.

Example 363

[1326] A 1.5 mg (2.4×10⁻⁶ mol) sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ and200 mL of dry toluene was added to a Parr® 1000 mL stirred autoclaveunder an argon atmosphere. The reactor was heated to 80° C. and purgedwith ethylene before addition of 3.0 mL of a 7% MMAO solution inheptane. The autoclave was rapidly pressurized with ethylene to 2.1 MPa.After 10 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 1.05 g(0.9×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately−25° C. with a maximum at 36° C.

Example 364

[1327] A standard solution of [(2,6-i-PrPh)₂DABAn]NiBr₂ was prepared asfollows: 1,2-difluorobenzene (10 mL) was added to 6.0 mg of[(2,6-i-PrPh)₂DABAn]NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask.The standard solution was transferred to a Kontes flask and stored underan argon atmosphere.

[1328] A 250 mL Schlenk flask was charged with 1 mL of a standardsolution of [(2,6-i-PrPh)₂DABAn]NiBr₂ (8.3×10⁻⁷ mol), and 100 mL of dry,deaerated toluene. The flask was cooled to −20° C. in a dry iceisopropanol bath and filled with ethylene (100 kPa, absolute) beforeaddition of 1.5 mL of a 10% MAO solution in toluene. After 30 min,acetone and water were added to quench the reaction. Solid polyethylenewas recovered from the flask collected and washed with 6 M HCl, H₂O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 0.8 g (7×10⁴ TO/h) of polyethylene. GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n)=519,000; M_(w)=768,000;M_(w)/M_(n)=1.48.

Example 365

[1329] A 250 mL Schlenk flask was charged with 20 mg of[(2,6-i-PrPh)₂DABMe₂]NiBr₂ (3.2×10⁻⁵ mol), and 75 mL of dry, deaeratedtoluene. The flask was cooled to 0° C. filled with propylene (100 kPaabsolute) before addition of 1.5 mL of a 10% MAO solution in toluene.After 30 min, acetone and water were added to quench the reaction. Solidpolypropylene was recovered from the flask and washed with 6 M HCl, H₂O,and acetone. The resulting polymer was dried under high vacuum overnightto yield 0.15 g polypropylene. DSC: T_(g)=−31° C. GPC (trichlorobenzene,135° C., polystyrene reference): M_(n)=25,000; M_(w)=37,000;M_(w)/M_(n)=1.47.

Example 366

[1330] Cyclopentene (16 μL, 10 eq) was added to a suspension of[(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene.A 10% MAO solution (1.5 mL) in toluene was added and the homogenousmixture stirred for 2 h at 25° C. After 2 h, the flask was filled withethylene (100 kPa, absolute) and the reaction stirred for 15 min.Acetone and water were added to quench the polymerization andprecipitate the polymer. Solid polyethylene was recovered from the flaskcollected and washed with 6 M HCl, H₂O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 3.6 g (32,000TO/h) polyethylene. GPC: (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n)=87,000; M_(w)=189,000; M_(w)/M_(n)=2.16. Acontrol experiment was run under identical conditions to that describedabove except no cyclopentene was added to stabilize the activated nickelcomplex. Polyethylene (380 mg, 3500 TO/h) was isolated. This exampledemonstrates the applicability of the Ni agostic cation as a potentialsoluble stable initiator for the polymerization of ethylene and otherolefin monomers.

Example 367

[1331] 1-Hexene (3 mL, 6 vol %) was added to a suspension of[(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene.The flask was cooled to −20° C. in a dry ice isopropanol bath and 1.5 mLof a 10% MAO solution in toluene was added. After stirring the reactionfor 1.5 h, acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-hexene) was recovered from theflask collected and washed with 6 M HCl, H₂O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 200 mgpoly(1-hexene). GPC (trichlorobenzene, 135° C., polystyrene reference):M_(n)=44,000; M_(w)=48,000; M_(w)/M_(n)=1.09.

Example 368

[1332] 1-Hexene (2.5 mL, 6 vol %) was added to a suspension of[(2,6-i-PrPh)₂DABAn]NiBr₂ (6 mg, 8.3×10⁻⁶ mol) in 50 mL of dry toluene.The flask was cooled to −10° C. in a dry ice isopropanol bath and 1.5 mLof a 7% MMAO solution in heptane was added. After stirring the reactionfor 1 h, acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-hexene) was recovered from theflask and washed with 6 M HCl, H₂O, and acetone. The resulting polymerwas dried under high vacuum overnight to yield 250 mg poly(l-hexene).GPC (dichloromethane, polystyrene reference): M_(n)=51,000;M_(w)=54,000; M_(w)/M_(n)=1.06.

Example 369

[1333] Propylene (1 atm) was added to a Schlenk flask charged with asuspension of [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) in 50 mLof dry toluene after cooling the mixture to −15° C. in a dry iceisopropanol bath. A 7% MMAO solution in heptane was added. Afterstirring the reaction for 30 min, acetone and water were added to quenchthe polymerization and precipitate the polymer. Solid polypropylene wasrecovered from the flask and washed with 6 M HCl, H₂O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 800 mgpolypropylene. GPC (dichloromethane, polystyrene reference):M_(n)=84,000; M_(w)=96,000; M_(w)/M_(n)=1.14

Example 370

[1334] Propylene (100 kPa, absolute) was added to a Schlenk flaskcharged with a suspension of [(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵mol) in 50 mL of dry toluene. After cooling the mixture to −15;C in adry ice isopropanol bath, a 7% MMAO solution in heptane was added. Afterstirring the reaction for 30 min, 5 mL of dry 1-hexene was added and thepropylene removed in vacuo. The polymerization was allowed to stir foran additional 30 min before acetone and water were added to quench thepolymerization and precipitate the polymer. Solidpolypropylene-b-poly(1-hexene) was recovered from the flask and washedwith 6 M HCl, H₂O, and acetone. The resulting polymer was dried underhigh vacuum overnight to yield 1.8 g polypropylene-b-poly(1-hexene). GPC(dichloromethane, polystyrene reference): M_(n)=142,000; M_(w)=165,000;M_(w)/M_(n)=1.16. ¹H-NMR analysis: indicates the presence of both apolypropylene and poly(1-hexene) block. ¹H-NMR also suggests that the DPof the propylene block is substantially higher than the DP of the1-hexene block. DSC analysis: T_(g)=−18° C. corresponding to thepolypropylene block. No other transitions were observed.

Example 371

[1335] 1-Octadecene (4 mL, 8 vol %) was added to a suspension of[(2,6-i-PrPh)₂DABAn]NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene.The flask was cooled to −10° C. in a dry ice isopropanol bath and 2 mLof a 7% MMAO solution in heptane was added. After stirring the reactionfor 1 h, acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-octadecene) was recovered from theflask collected and washed with 6 M HCl, H₂O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 200 mgpoly(1-octadecene). GPC (trichlorobenzene, 135° C., polystyrenereference): M_(n)=19,300; M_(w)=22,700; M_(w)/M_(n)=1.16. DSC: T_(m)=37°C. ¹H-NMR (CDCl₃) analysis 47 branches/1000 C (theoretical 56branches/1000 C).

Example 372

[1336] A 12-mg (0.022 mmol) sample of [(para-Me-Ph)₂DABMe₂]NiBr₂ wasplaced in a Parr® 1000 mL stirred autoclave under an argon atmospherewith 200 mL of dry toluene (reactor temperature was 65° C.). The reactorwas purged with ethylene and 1.5 mL (100 eq) of a 10% MAO solution intoluene was added to the suspension. The autoclave was rapidlypressurized to 5.5 MPa and the reaction was stirred for 60 min. A 15° C.exotherm was observed. The oligomerization was quenched upon addition ofacetone and water. The solvent was removed in vacuo resulting in 20 g ofethylene oligomers. ¹HNMR (CDCl₃) analysis 83% α-olefin.

Example 373

[1337] A 12-mg (0.022 mmol) sample of [Ph2DABAn]NiBr₂ was placed in aParr® 1000 mL stirred autoclave under an argon atmosphere with 200 mL ofdry toluene (reactor temperature was 55° C.). The reactor was purgedwith ethylene and 2 mL (100 eq) of a 7% MMAO solution in heptane wasadded to the suspension. The autoclave was rapidly pressurized to 5.5MPa and the reaction was stirred for 60 minutes. A 18° C. exotherm wasobserved. The oligomerization was quenched upon addition of acetone andwater. The solvent was removed in vacuo resulting in 26 g (corrected forloss of C₄, C₆, and C₈ during work-up) of ethylene oligomers. ¹H-NMR(CDCl₃) and GC analysis: Distribution: C₄-C₁₈, C₄=6.0%, C₆=21%, C₈=22%,C₁₀=17%, C₁₂=16%, C₁₄=13%, C₁₆=5%, C₁₈=trace; 90% α-olefin.

Example 374

[1338] A 12-mg (0.022 mmol) sample of [Ph2DABAn]NiBr₂ was placed in aParr® 1000 mL stirred autoclave under an argon atmosphere with 200 mL ofdry toluene (reactor temperature was 45° C.). The reactor was purgedwith ethylene and 2 mL (100 eq) of a 7% MMAO solution in heptane wasadded to the suspension. The autoclave was rapidly pressurized to 5.5MPa and the reaction was stirred for 60 min. The oligomerization wasquenched upon addition of acetone and water. The solvent was removed invacuo resulting in 32 g (corrected for loss of C₄, C₆, and C₈ duringwork-up) of ethylene oligomers. ¹H-NMR (CDCl₃) and GC analysis:Distribution: C₄-C₂₀, C₄=9.0%, C₆=19%, C₈=19%, C₁₀=15%, C₁₂=14%,C₁₄=11%, C₁₆=5%, C₁₈=4%, C₂₀=2%; 92% α-olefin.

Example 375

[1339] A 12-mg (0.022 mmol) sample of [(Ph)DABAn]NiBr₂ was placed in a1000 mL stirred autoclave under an argon atmosphere with 200 mL ofdeaerated toluene (reactor temperature was 25° C.). The reactor waspurged with ethylene and 2 mL (100 eq) of a 10% MAO solution in toluenewas added to the suspension. The autoclave was rapidly pressurized to2.1 MPa and the reaction was stirred for 30 min. A 20° C. exotherm wasobserved. The oligomerization was quenched upon addition of acetone andwater. The solvent was removed in vacuo resulting in 16.1 g of afluid/waxy mixture (50,000 TO/h based on isolated oligomer). ¹H-NMR(CDCl₃) analysis 80% α-olefin. Distribution of isolated oligomers by GCanalysis: C₁₀=20%, C₁₂=28%, C₁₄=23%, C₁₆=15%, C₁₈=10%, C₂₀=4%. All C₄,C₆, C₈ and some C₁₀ was lost during work-up.

Example 376

[1340] A 12-mg (0.022 mmol) sample of [(Ph)DABAn]NiBr₂ was placed in a1000 mL stirred autoclave under an argon atmosphere with 200 mL ofdeaerated toluene (reactor temperature was 25° C.). The reactor waspurged with ethylene and 2 mL (100 eq) of a 10% MAO solution in toluenewas added to the suspension. The autoclave was rapidly pressurized to4.1 MPa and the reaction was stirred for 60 minutes. A 20° C. exothermwas observed. The oligomerization was quenched upon addition of acetoneand water. The solvent was removed in vacuo resulting in 28.3 g of crudeproduct (50,000 TO/h based on isolated oligomer). Trace Al was removedby an aqueous/organic work-up of the crude mixture. ¹H-NMR (CDCl₃)analysis 85% α-olefin. Distribution of isolated oligomers by GCanalysis: C₁₀=13%, C₁₂=30%, C₁₄=26%, C₁₆=18%, C₁₈=10%, C₂₀=3%. All C₄,C₆, C₈ and some C₁₀ was lost during work -up.

Example 377

[1341] A 12-mg (0.022 mmol) sample of [(Ph)DABAn]NiBr₂ was placed in a1000 mL stirred autoclave under an argon atmosphere with 200 mL ofdeaerated toluene (reactor temperature was 25° C.). The reactor waspurged with ethylene and 2 mL (100 eq) of a 10% MAO solution in toluenewas added to the suspension. The autoclave was rapidly pressurized to6.7 MPa and the reaction was stirred for 60 min. A 15° C. exotherm wasobserved. The oligomerization was quenched upon addition of acetone andwater. The solvent was removed in vacuo resulting in 21.6 g of crudeproduct (40,000 TO/h based on isolated oligomer). ¹H-NMR (CDCl₃)analysis 93% α-olefin. Distribution of isolated oligomers by GCanalysis: C₁₀=13%, C₁₂=27%, C₁₄=26%, C₁₆=18%, C₁₈=12%, C₂₀=5%. All C₄,C₆, C₈ and some C₁₀ was lost during work-up.

Example 378

[1342] A 12-mg (0.022 mmol) sample of [Ph₂DABAn]NiBr₂ was placed in a1000 mL stirred autoclave under an argon atmosphere with 200 mL of drytoluene (reactor temperature was 50° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 10% MAO solution in toluene was added tothe suspension. The autoclave was rapidly pressurized to 5.5 MPa and thereaction was stirred for 60 minutes. A 15° C. exotherm was observed. Theoligomerization was quenched upon addition of acetone and water. Thesolvent was removed in vacuo resulting in 22.3 g of crude product(40,000 TO/h based on isolated oligomer). ¹H-NMR (CDCl₃) analysis 92%α-olefin. Distribution of isolated oligomers by GC analysis: C₁₀=10%,C₁₂=28%, C₁₄=25%, C₁₆=19%, C₁₈=12%, C₂₀=6%. All C₄, C₆, C₈ and some C₁₀was lost during work-up.

Examples 379-393

[1343] General Procedure for Copolymerizations

[1344] (a) Experiments at Ambient Pressure: A Schlenk flask containingthe catalyst precursor was cooled to −78° C., evacuated, and placedunder an ethylene atmosphere. In subsequent additions, methylenechloride and the acrylate were added to the cold flask via syringe. Thesolution was allowed to warm to room temperature and stirred with amagnetic stir bar. After the specified reaction time, the reactionmixture was added to ˜600 mL of methanol in order to precipitate thepolymer. Next, the methanol was decanted off of the polymer, which wasthen dissolved in ˜600 mL of Et₂O or petroleum ether. (Forcopolymerizations with FOA, a second precipitation of the polymersolution into methanol was often necessary in order to remove all of theacrylate from the polymer.) The solution was filtered though a plug ofCelite® and/or neutral alumina, the solvent was removed, and the polymerwas dried in vacuo for several days. The copolymers were isolated asclear, free-flowing or viscous oils. The copolymers were often darkenedby traces of palladium black, which proved difficult to remove in somecases. Polymers with high FOA incorporation were white, presumably dueto phase separation of the fluorinated and hydrocarbon segments.

[1345] (b) Experiments at Elevated Pressure: Reactions were carried outin a mechanically stirred 300 mL Parr® reactor, equipped with anelectric heating mantle controlled by a thermocouple dipping into thereaction mixture. A solution of 0.1 mmol of catalyst precursor inmethylene chloride, containing the functionalized comonomer (5-50 mL,total volume of the liquid phase: 100 mL), was transferred via cannulato the reactor under a nitrogen atmosphere. After repeatedly flushingwith ethylene or propylene, constant pressure was applied bycontinuously feeding the gaseous olefin and the contents of the reactorwere vigorously stirred. After the specified reaction time, the gas wasvented. Volatiles were removed from the reaction mixture in vacuo, andthe polymer was dried under vacuum overnight. In representative runs,the volatile fraction was analyzed by GC for low-molecular-weightproducts. Residual monomers (tBuA, FOA) or homooligomers of thefunctionalized comonomer (MVK) were removed by precipitating the polymerfrom methylene chloride solution with methanol. This procedure did notsignificantly alter the polymer composition.

[1346] Copolymer Spectral Data. In addition to the signals of themethyl, methylene and methine groups originating from ethylene orpropylene, the ¹H and ¹³C NMR spectra of the copolymers exhibitcharacteristic resonances due to the functionalized comonomer. TheIR-spectra display the carbonyl band of the functional groupsoriginating from the comonomer.

[1347] Ethylene-MA Copolymer: ¹H NMR (CDCl₃, 400 MHz) δ3.64 (s, OCH₃),2.28 (t, J=7, CH₂C(O)), 1.58 (m, CH₂CH₂C(O)); ¹³C NMR (C₆D₆, 100 MHz)δ176 (C(O)), 50.9 (OCH₃); IR (film): 1744 cm⁻¹ [ν(C(O))].

[1348] Ethylene-FOA Copolymer: ¹H NMR (CDCl₃, 400 MHz) δ4.58 (t,J_(HF)=14, OCH₂(CF₂)₆CF₃), 2.40 (t, J=7, CH₂C(O)), 1.64 (m, CH₂CH₂C(O));¹³C NMR (CDCl₃, 100 MHz) δ172.1 (C(O)), 59.3 (t, J_(CF)=27,OCH₂(CF₂)₆CF₃); IR (film): 1767 cm⁻¹ [ν(C(O))].

[1349] Ethylene-tBuA Copolymer: ¹H NMR (CDCl₃, 300 MHz) δ2.18 (t, J=7,CH₂C(O)), 1.55 (m, CH₂CH₂C(O)), 1.42 (s, OCMe₃); ¹³C NMR (CDCl₃, 62 MHz)δ173.4 (C(O)); IR (film): 1734 cm⁻¹ (CO).

[1350] Ethylene-MVK Copolymer: ¹H NMR (CDCl₃, 250 MHz) δ2.39 (t, J=7,CH₂C(O)), 2.11 (s, C(O)CH₃), 1.5 (m, CH₂CH₂C(O)); ¹³C NMR (CDCl₃, 62MHz) δ209 (C(O)); IR (film): 1722 cm⁻¹ [ν(C(O))].

[1351] Propylene-MA Copolymer: ¹H NMR (CDCl_(3, 250) MHz) δ3.64 (s,OCH₃), 2.3 (m, CH₂C(O)); ¹³C NMR (CDCl₃, 62 MHz) δ174.5 (C(O)), 51.4(OCH₃); IR (film): 1747 cm⁻¹ [ν(C(O))].

[1352] Propylene-FOA Copolymer: ¹H NMR (CDCl₃, 250 MHz) 6 4.57 (t,J_(HF)=14, OCH₂(CF₂)₆CF₃), 2.39 (m, CH₂C(O)); 13C NMR (CDCl₃, 62 MHz)δ172.2 (C(O)), 59.3 (t, J_(CF)=27, OCH₂(CF₂)₆CF₃); IR (film): 1767 cm⁻¹[ν(C(O))].

[1353] Results of the various polymerization are given in the Tablebelow. react. results polymer Ex. monomers conc. mass comon.- TON^(e)M_(n)f 379 6b E/MA 0.6 M 2 22.2 1.0% 7710 78 88 1.8 380 6b E/MA 2.9 M 24.3 6.1% 1296 84 26 1.6 381 6b E/MA 5.8 M 2 1.8 12.1%  455 63 11 1.6 3826b E/MA 5.8 M 6 11.2 4.0% 3560 148 42 1.8 383 6a E/MA 5.8 M 6 1.2 5.0%355 19 0.3^(g) — 384 6b E/MA 5.8 M 6 1.2 4.7% 364 18 10 1.8 385 6bE/tBuA 3.4 M 6 2.8 0.7% 956 7 25 1.6 386 6b E/tBuA 0.4 M 1 1.9 0.4% 6653 6 1.8 387 1a E/FOA 0.6 M 1 1.5 0.3% 506 2 3 1.6 388 1b E/FOA 0.6 M 127.5 0.6% 8928 55 106 3.1 389 6b E/FOA 1.8 1 9.5 0.9% 2962 27 95 2.7 3906b E/MVK 3.0 M 6 1.8 1.3% 626 8 7 1.5 391 6b E — 6 10.3 — 37127 384 3.1392 6b P/MA 0.6 M 6 5.0 1.1% 1179 13 37 1.8 393 6b P/FOA 1.8 M 2 1.05.6% 145 9 18 1.8

Example 394

[1354] Et₂O (30 mL) was added to a round bottom flask containing 445 mg(1.10 mmol) of (2,6-i-PrPh)₂DABMe₂ and 316 mg (1.15 mmol) of Ni(COD)₂.Methyl acrylate (100 μL) was then added to the flask via microlitersyringe. The resulting blue solution was stirred for several hoursbefore the Et₂O was removed in vacuo. The compound was then dissolved inpetroleum ether and the resulting solution was filtered and then cooledto −35° C. in the drybox freezer. Purple single crystals of[(2,6-i-PrPh)₂DABMe₂]Ni[H₂C═CHCO(OMe)] were isolated:

[1355]¹H NMR (CD₂Cl₂, 300 MHz, −40° C.) δ7.4-7.2 (m, 6, H_(aryl)), 3.74(br septet, 1, CHMe₂), 3.09 (septet, 1, J=6.75, C′HMe₂), 2.93 (septet,1, J=6.75, C″HMe₂), 2.85 (s, 3, OMe), 2.37 (br septet, 1, C′″HMe₂), 2.10(dd, 1, J=13.49, 8.10, H₂C═CHC(O)OMe), 1.66 (dd, 1, J=13.49, 4.05,HH′C═CHC(O)OMe), 1.41 (d, 3, J=6.75, CHMeMe′), 1.35 (dd, 1, J=8.10,4.05, HH′C═CHC(O)OMe), 1.26 (d, 3, J=8.10, C″HMeMe′), 1.24 (d, 3,J=8.09, C′HMeMe′), 1.13 (d, 3, J=6.75, C′HMeMe′), 1.09-1.03 (doublets,12, CHMeMe′, C″HMeMe′, C′″HMeMe′), 0.79 and 0.62 (s, 3 each,N═C(Me)—C′(Me)═N); ¹³C NMR (CD₂Cl₂, 300 MHz, −20° C.) δ174.2 (C(O)OMe),166.6 and 165.5 (N═C—C′═N), 147.9 and 146.8 (Ar, Ar′: C_(ipso)), 139.5,139.0, 138.2 and 137.7 (Ar: C_(o), C′_(o) and Ar′: C_(o), C′_(o)), 125.6and 125.4 (Ar, Ar′: C_(p)), 123.5, 123.4, 123.3 and 123.0 (Ar: C_(m),C′_(m) and Ar′: C_(m), C′_(m)), 49.9 and 39.8 (H₂C═CHC(O)OMe), 28.8,28.5, 28.4 and 28.3 (CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 26.1(H₂C═CHC(O)OMe), 24.3, 23.8, 23.6, 23.4, 23.0, 22.9, 22.7 and 22.7(CHMeMe′, C′HMeMe′, C″HMeMe′, C′″HMeMe′), 20.21 and 20.16(N═C(Me)—C′(Me)═N).

Example 395

[1356] In a nitrogen-filled drybox, 289 mg (0.525 mmol) of[(2,6-i-PrPh)₂DABMe₂Ni(H₂C═CHCO(OMe))] and 532 mg (0.525 mmol) ofH(OEt₂)₂BAF were placed together in a round bottom flask. The flask wascooled in the −35° C. freezer before adding 20 mL of cold (−35° C.) Et₂Oto it. The reaction mixture was then allowed to warm to room temperatureas it was stirred for 2 h. The solution was then filtered and thesolvent was removed in vacuo to yield 594 mg (80.1%) of the 4-memberedchelate, {[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF, as a burnt orangepowder: ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ7.72 (s, 8, BAF: H_(o)), 7.56 (s,4, BAF: H_(p)), 7.5-7.2 (m, 6, H_(aryl)), 3.52 (S, 3, OMe), 3.21 (q, 1,J=6.75, CHMeC(O)OMe), 3.45, 3.24, 3.02 and 3.02 (septet, 1 each, CHMe₂,C′HMe₂, C″HMe₂ and C′″HMe₂), 2.11 and 2.00 (s, 3 each,N═C(Me)—C′(Me)═N), 1.55, 1.50, 1.47, 1.33, 1.28, 1.24, 1.23 and 1.17 (d,3 each, CHMeMe′, C′HMeMe′, C″HMeMe′ and C′″HMeMe′), −0.63 (d, 3, J=6.75,CHMeC(O)OMe); ¹³C NMR (CD₂Cl₂, 300 MHz, rt) δ178.2, 177.0 and 174.1(C(O)OMe, N═C—C′═N), 162.2 (q, J_(CB)=49.7, BAF: C_(ipso)), 141.2 and139.8 (Ar, Ar′: C_(ipso)), 139.4, 138.89, 138.79 and 138.40 (Ar, Ar′:C_(o), C_(o)′), 135.2 (BAF: C_(o)), 130.0 and 129.6 (Ar, Ar′: C_(p),C_(p)′), 129.3 (q, BAF: C_(m)), 125.6, 125.2, 125.0 and 124.7 (Ar, Ar′:C_(m), C′_(m)), 125.0 (q, J_(CF)=272.5, BAF: CF₃), 117.9 (BAF: C_(p)),53.6 (OMe), 30.3, 30.0, 29.9 and 29.8 (CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂),24.5, 24.1, 24.0, 23.7, 23.33, 23.26, 23.1 and 23.1 (CHMeMe′, C′HMeMe′,C″HMeMe′, C′″′HMeMe′), 20.6 and 19.5 (N═C—C′═N), 6.9 (CHMeC(O)O Me).

Examples 396-400

[1357] Polymerization of ethylene by {[(2,6-i-PrPh)₂DABMe₂]Ni [CHMeC(O)OMe]}BAF. This compound was used to catalyze the polymerization ofpolyethylene at temperatures between RT to 80° C. Addition of a Lewisacid often resulted in improved yields of polymer.

[1358] General Polymerization Procedure for Examples 396-400. In thedrybox, a glass insert was loaded with{[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF. In addition, 2 equiv of aLewis acid (when used) was added to the insert. The insert was cooled to−35° C. in a drybox freezer, 5 mL of deuterated solvent was added to thecold insert, and the insert was then capped and sealed. Outside of thedrybox, the cold tube was placed under 6.9 MPa of ethylene and allowedto warm to RT or 80° C. as it was shaken mechanically for 18 h. Analiquot of the solution was used to acquire a ¹H NMR spectrum. Theremaining portion was added to ˜20 mL of MeOH in order to precipitatethe polymer. The polyethylene was isolated and dried under vacuum.

Example 396

[1359] Polymerization Conditions:{[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF (84.8 mg, 0.06 mmol); No LewisAcid; C₆D₆; RT. No polymer was isolated and polymer formation was notobserved in the ¹H NMR spectrum.

Example 397

[1360] Polymerization Conditions:{[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF (84.8 mg, 0.06 mmol); 2 EquivBPh₃; C₆D₆, RT. Solid white polyethylene (0.91 g) was isolated.

Example 398

[1361] Polymerization Conditions:{[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF (84.8 mg, 0.06 mmol); 2 EquivB[3,5-trifluoromethylphenyl]₃; C₆D₆, RT. Solid white polyethylene (0.89g) was isolated.

Example 399

[1362] Polymerization Conditions: {[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF; 2 Equiv BPh₃; C₆D₆, 80° C. Polyethylene (4.3 g) wasisolated as a spongy solid.

Example 400

[1363] Polymerization Conditions:{[(2,6-i-PrPh)₂DABMe₂]Ni[CHMeC(O)OMe]}BAF (84.8 mg, 0.06 mmol); No LewisAcid; CDCl₃, 80° C. Polyethylene (2.7 g) was isolated as a spongy solid.

Example 401

[1364] An NMR tube was loaded with {[(2,6-i-PrPh)₂DABH₂]NiMe(OEt₂)}BAF.The tube was capped with a septum, the septum was wrapped withParafilm®, and the tube was cooled to −78° C. CD₂Cl₂ (700 μL) and oneequiv of methyl acrylate were added to the cold tube in subsequentadditions via gastight microliter syringe. The tube was transferred tothe cold NMR probe. Insertion of methyl acrylate and formation of the4-membered chelate complex, {[(2,6-i-PrPh)₂DABH₂]Ni[CHEtC(O)OMe]}BAF,was complete at −10° C.:

[1365]¹H NMR (CD₂Cl₂, 400 MHz, −10° C.) δ8.23 and 8.03 (s, 1 each,N═C(H)—C′(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.55 (s, 4, BAF: H_(p)),7.5-7.2 (m, 6, H_(aryl)), 3.69, 3.51, 3.34 and 3.04 (septet, 1 each,CHMe₂, C′HMe₂, C″HMe₂ and C′41 HMe₂), 3.58 (s, 3, OMe) , 1.48, 1.46,1.46, 1.45, 1.30, 1.27, 1.193 and 1.189 (d, 3 each, J=6.5-7.3, CHMeMe′,C′HMeMe′, C″HMeMe′ and C′″HMeMe′), 0.79 and −0.52 (m, 1 each,CH(CHH′CH₃), 0.68 (t, 3, J=6.9, CH(CH₂CH₃), (CHEt signal was notassigned due to overlap with other protons).

Example 402

[1366] A solution of the 4-membered chelate complex{([(2,6-i-PrPh)₂DABH₂]Ni[CHEtC(O)OMe]}BAF was allowed to stand at RT for1 day. During this time, conversion to the 6-membered chelate complex,{[(2,6-i-PrPh)₂DABH₂]Ni[CH₂CH₂CH₂C(O)OMe]}BAF, was complete: ¹H NMR(CD₂Cl₂, 400 MHz, rt) δ8.47 and 8.01 (s, 1 each, N═C(H)—C′(H)═N), 7.72(s, 8, BAF: H_(o)), 7.56 (s, 4, BAF: H_(p)), 7.5-7.0 (m, 6, H_(aryl)),3.61 (s, 3, OMe), 3.45 and 3.09 (septet, 2 each, CHMe₂ and C′HMe₂), 2.25(t, 2, J 7.3, CH₂C(O)), 1.61 (pentet, 2, J=7.3, NiCH₂CH₂CH₂), 1.50,1.50, 1.46, and 1.30 (d, 6 each, J=6.8-6.9, CHMeMe′, C′HMeMe′), 0.92 (t,2, J=7.4, NiCH₂).

Examples 403-407

[1367] These Examples illustrate the formation of metallacycles of theformula shown on the right side of the equation, and the use of thesemetallacycles as polymerization catalysts.

[1368] (R═H, Me, An; M═Ni, Pd)

[1369] In the absence of olefin, the ether-stabilized catalystderivatives were observed to decompose in CD₂Cl₂ solution with loss ofmethane. For the catalyst derivative where M═Pd and R═H, methane losswas accompanied by clean and selective formation of the metallacycleresulting from C—H activation of one of the aryl i-propyl substituents.This metallacycle could be isolated, although not cleanly, as itsinstability and high solubility prevented recrystallization. Also itcould be converted to another metallacycle in which the diethyl etherligand is replaced by an olefin ligand, especially ethylene.

Example 403

[1370] A 700 μL CD₂Cl₂ solution of {[(2,6-i-PrPh)₂DABH₂]PdMe(OEt₂)}BAF(68.4 mg) was allowed to stand at room temperature for several hours andthen at −30° C. overnight. Such highly concentrated solutions of theresulting metallacycle wherein R is H and M is Pd were stable for hoursat room temperature, enabling ¹H and 13C NMR spectra to be acquired: ¹HNMR (CD₂Cl₂, 400 MHz, 41° C.) δ8.17 (s, 2, N═C(H)—C′(H)═N), 7.75 (s, 8,BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)), 7.5-7.0 (m, 6, H_(aryl)), 3.48 (q,4, J=6.88, O(CH₂CH₃)₂), 3.26 (septet, 1, J=6.49, CHMe₂), 3.08 (septet,1, J=6.86, C′HMe₂), 2.94 (septet, 1, J=6.65, C″HMe₂), 2.70 (dd, 1,J=6.67, 0.90, CHMeCHH′Pd), 2.43 (dd, 1, J=7.12, 4.28, CHMeCHH′Pd), 2.23(br m, 1, CHMeCH₂Pd), 1.54 (d, 3, J=6.86, CHMeCH₂Pd), 1.43 (d, 3,J=6.79, C″HMeMe′), 1.40 (d, 3, J=7.12, CHMeMe′), 1.37 (d, 3, J=6.95,C¹HMeMe′), 1.27 (d, 6, J=6.79, C′HMeMe′, C″HMeMe′), 1.12 (d, 3, J=6.54,CHMeMe′), 1.23 (br m, 6, O(CH₂CH₃)₂), 0.21 (CH₄); ¹³C NMR (CD₂Cl₂, 400MHz, 41° C.) δ162.5 (J_(CH)=181.5, N═C(H)), 162.3 (q, J_(BC)=49.8, BAF:C_(ipso)), 161.2 (J_(CH)=178.4, N═C′(H)), 145.8 and 144.5 (Ar, Ar′:C_(ipso)), 141.6, 140.7, 140.3 and 138.8 (Ar, Ar′: C_(ipso)), 135.3(BAF: C_(o)), 131.6 and 129.8 (Ar, Ar′: C_(p)), 129.4 (q, J_(CF)=29.9,BAF: CF₃), 128.1, 127.6, 125.2 and 124.5 (Ar, Ar′: C_(o), C_(o)′), 125.1(BAF: CF₃), 118.0 (BAF: C_(p)), 72 (br, O(CH₂CH₃)₂), 43.2 (CHMeCH₂Pd),40.5 (CHMeCH₂Pd), 29.5,. 29.1 and 28.8 (CHMe₂, C′HMe₂, C″HMe₂), 26.2(br), 25.3, 25.2, 25.1, 24.5 (br), 23.3 and 22.1 (CHMeMe′, C′HMeMe′,C″HMeMe′, CHMeCH₂Pd), 15.5 (br, O(CH₂CH₃)₂), −14.8 (CH₄).

Example 404

[1371] Addition of ethylene to a CD₂Cl₂ solution of the compoundprepared in Example 403 resulted in loss of ether and formation of thecorresponding ethylene adduct (spectral data: see Example 405.) Warmingof the ethylene adduct in the presence of excess ethylene resulted inbranched polymer formation: 1.3 ppm (CH₂)_(n), 0.9 ppm (CH₃). For theethylene polymerization initiated by this metallacycle, rates ofinitiation were significantly slower than rates of propagation.

Example 405

[1372] The metallacycle of Example 403 wherein the diethyl ether ligandwas replaced by an ethylene ligand was stable enough so that NMR spectracould be obtained. ¹H NMR (CD₂Cl₂, 400 MHz, −61° C.) δ8.25 and 8.23(N═C(H)—C′(H)═N), 7.74 (s, 8, BAF: H_(o)), 7.55 (s, 4, BAF: H_(p)),7.55-7.16 (m, 6, H_(aryl)), 4.67 (m, 2, HH′C═CHH′), 4.40 (m, 2,HH′C═CHH′), 2.95 (septet, 1, J=6.30, CHMe₂), 2.80 (septet, 2, J=6.36,C′HMe₂ and C″HMe₂), 2.53 (br m, 1, CHMeCH₂Pd), 2.43 (d, 1, J=8.16,CHMeCHH′Pd), 1.73 (dd, 1, J=8.16, 2.84, CHMeCHH′Pd), 1.45 and 1.19 (d, 3each, J=6.79-6.40, CHMeMe′), 1.42 (d, 3, J=7.05, CHMeCH₂Pd), 1.30, 1.30,1.19 and 0.99 (d, 3 each, J=6.40-6.65, C′HMeMe′ and C″HMeMe′); ¹³C NMR(CD₂Cl₂, 400 MHz, −61° C.) δ162.7 (J_(CH)=179.7, N═CH), 162.1(J_(CH)=180.9, N═C′H), 161.6 (q, J_(CB)=49.7, BAF: C_(ipso)), 144.7,141.7, 141.2, 139.2, 137.5 and 137.1 (Ar, Ar′: C_(ipso), C_(o), C_(o)),134.6 (BAF: C_(o)), 131.0 and 129.0 (Ar, Ar′: C_(p)), 128.6 (q, BAF:C_(m)), 124.4 (q, J_(CF)=272.5, BAF: CF₃), 124.6 and 124.0 (Ar, Ar′:C_(m)), 117.4 (BAF: C_(p)), 92.3 (J_(CH)=162.4, H₂C═CH₂), 45.1 (CH₂Pd),41.1 (CHMeCH₂Pd), 28.9, 28.5 and 28.2 (CHMe₂, C′HMe₂, C″HMe₂), 26.1,25.6, 25.1, 24.9, 24.6, 22.9 and 21.4 (CHMeMe′, C′HMeMe′, C″HMeMe′,CHMeCH₂Pd).

Example 406

[1373] In a nitrogen-filled drybox, 30 mL of THF was added to a flaskcontaining (2,6-i-PrPh)₂DABAn (1.87 g, 3.72 mmol) and Ni(COD)₂ (1.02 g,3.72 mmol). The resulting purple solution was stirred for several hoursbefore removing the solvent in vacuo. The product was dissolved in aminimum amount of pentane and the resulting solution was filtered andthen placed in the drybox freezer (−35° C.) to recrystallize. Purplecrystals of [(2,6-i-PrPh)₂DABAn]Ni(COD) were isolated (1.33 g, 53.5%,first crop). ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ7.77 (d, 2, J=8.06,H_(aryl)), 7.44 (t, 2, J=7.52, H_(aryl)), 7.33 (d, 2, J=7.70, H_(aryl)),6.89 (t, 2, J=7.70, H_(aryl)), 6.13 (d, 2, J=6.13, H_(aryl)), 3.93 (brs, 4, COD: —HC═CH—), 3.48 (septet, 4, J=6.87, CHMe₂), 2.54 (br m, 4,COD: —CHH′—), 1.51 (m, 4, COD: —CHH′—), 1.37 (d, 12, J=6.60, CHMeMe′),0.77 (d, 12, J=6.60, CHMeMe′); ¹³C NMR (CD₂Cl₂, 75.5 MHz, rt) δ151.7,151.6, 138.5, 137.1, 133.0, 132.1, 128.8, 125.6, 123.8, 123.7, 119.0(C_(aryl)), 88.7 (COD: —HC═CH—), 29.9 (COD: —CH₂—), 28.0, 25.1 and 23.8(CHMeMe′).

Example 407

[1374] In the drybox, a glass insert was loaded with 35.2 mg (0.0527mmol) of [(2,6-i-PrPh)₂DABAn]Ni(COD) and 55.2 mg (0.0545 mmol) ofH(OEt₂)₂BAF. The insert was cooled to −35° C. in the drybox freezer, 5mL of CDCl₃ was added to the cold insert, and the insert was then cappedand sealed. Outside of the drybox, the cold tube was placed under 6.9MPa of ethylene and allowed to warm to rt as it was shaken mechanicallyfor 18 h. An aliquot of the solution was used to acquire a ¹H NMRspectrum. The remaining portion was added to ˜20 mL of MeOH in order toprecipitate the polymer. The polyethylene (6.1 g) was isolated and driedunder vacuum.

Examples 408-412

[1375] (acac)NiEt(PPh3) was synthesized according to publishedprocedures (Cotton, F. A.; Frenz, B. A.; Hunter, D. L. J. Am. Chem. Soc.1974, 96, 4820-4825).

[1376] General Polymerization Procedure for Examples 408-412. In thedrybox, a glass insert was loaded with 26.9 mg (0.06 mmol) of(acac)NiEt(PPh3), 53.2 mg (0.06 mmol) of NaBAF, and 0.06 mmol of anα-diimine ligand. In addition, 2 equiv of a phosphine scavenger such asBPh₃ or CuCl was sometimes added. The insert was cooled to −35° C. inthe drybox freezer, 5 mL of C₆D₆ was added to the cold insert, and theinsert was then capped and sealed. Outside of the drybox, the cold tubewas placed under 6.9 MPa of ethylene and allowed to warm to RT as it wasshaken mechanically for 18 h. An aliquot of the solution was used toacquire a ¹H NMR spectrum. The remaining portion was added to ˜20 mL ofMeOH in order to precipitate the polymer. The polyethylene was isolatedand dried under vacuum.

Example 408

[1377] The α-diimine was (2,6-i-PrPh)₂DABMe₂. Solid white polyethylene(1.6 g) was isolated.

Example 409

[1378] The α-diimine was (2,6-i-PrPh)₂DABMe₂, and 29.1 mg of BPh₃ wasalso added. Solid white polyethylene (7.5 g) was isolated.

Example 410

[1379] The α-diimine was (2,6-i-PrPh)₂DABMe₂, and 11.9 of CuCl was alsoadded. Solid white polyethylene (0.8 g) was isolated.

Example 411

[1380] The α-diimine was (2,6-i-PrPh)₂DABAn. Solid white polyethylene(0.2 g) was isolated.

Example 412

[1381] The α-diimine was (2,6-i-PrPh)₂DABAn, and 29.1 mg of BPh₃ wasalso added. Solid white polyethylene (14.7 g) was isolated.

Examples 413-420

[1382] The following synthetic methods and polymerization procedureswere used to synthesize and test the polymerization activity of thefunctionalized α-diimine ligands of these Examples.

[1383] Synthetic Method A. One equiv of glyoxal or the diketone wasdissolved in methanol. Two equiv of the functionalized aniline was addedto the solution along with ˜1 mL of formic acid. The solution wasstirred until a precipitate formed. The precipitate was collected on afrit and washed with methanol. The product was then dissolved indichloromethane and the resulting solution was stirred overnight oversodium sulfate. The solution was filtered and the solvent was removed invacuo to yield the functionalized α-diimine.

[1384] Synthetic Method B. One equiv of glyoxal or the diketone wasdissolved in dichloromethane and two equiv of the functionalized anilinewas added to the solution. The reaction mixture was stirred over sodiumsulfate (˜1 week). The solution was filtered and the solvent was removedin vacuo. The product was washed or recrystallized from petroleum etherand then dried in vacuo.

[1385] Nickel Polymerization Procedure. In the drybox, a glass insertwas loaded with one equiv each of Ni(COD)₂, H(OEt₂)₂BAF, and theα-diimine ligand. The insert was cooled to −35° C. in the dryboxfreezer, 5 mL of C₆D₆ was added to the cold insert, and the insert wasthen capped and sealed. Outside of the drybox, the cold tube was placedunder 6.9 MPa of ethylene and allowed to warm to RT as it was shakenmechanically for 18 h. An aliquot of the solution was used to acquire a¹H NMR spectrum. The remaining portion was added to ˜20 mL of MeOH inorder to precipitate the polymer. The polyethylene was isolated anddried under vacuum.

[1386] Palladium Polymerization Procedure. In the drybox, a glass insertwas loaded with one equiv each of [CODPdMe(NCMe)]BAF and the α-diimineligand. The insert was cooled to −35° C. in the drybox freezer, 5 mL ofC₆D₆ was added to the cold insert, and the insert was then capped andsealed. Outside of the drybox, the cold tube was placed under 6.9 MPa ofethylene and allowed to warm to RT as it was shaken mechanically for 18h. An aliquot of the solution was used to acquire a ¹H NMR spectrum. Theremaining portion was added to ˜20 mL of MeOH in order to precipitatethe polymer. The polyethylene was isolated and dried under vacuum.

Example 413

[1387] α-Diimine was (2-hydroxyethylPh)₂DABMe₂. Synthetic Method B: ¹HNMR (CDCl₃, 300 MHz, rt) δ7.28-7.20 (m, 4, H_(aryl)), 7.12 (t, 2,J=7.52, H_(aryl)), 6.67 (d, 2, J=7.67, H_(aryl)), 3.74 (t, 4, J=6.79,CH₂OH), 3.11 (br s, 2, OH), 2.76 (t, 4, J=6.79, CH₂CH₂OH), 2.16 (s, 6,N═C(Me)—C(Me)═N); ¹³C NMR (CDCl₃, 75 MHz, rt) δ168.2 (N═C—C═N), 149.0(Ar: C_(ipso)), 128.4 (Ar: C_(o)), 130.4, 127.1, 124.6 and 118.2 (Ar:C_(m), C_(p), C_(m)′, C_(o)′), 62.9 (CH₂OH), 35.3 (CH₂CH₂OH), 15.8(N═C(Me)—C(Me)═N).

[1388] Nickel Polymerization Procedure: (0.02 mmol scale) Seventy mg ofpolyethylene was isolated. ¹H NMR spectrum (C₆D₆) shows the productionof 1- and 2-butenes along with smaller amounts of higher olefins.

[1389] Palladium Polymerization Procedure: (0.06 mmol scale) No polymerwas isolated, however, the ¹H NMR spectrum shows peaks consistent withthe formation of branched polyethylene: 1.3 ppm (CH₂)_(n), 0.9 ppm (CH₃of branches). Broad α-olefinic resonances are observed in the baseline.

Example 414

[1390] α-Diimine is (2,6-Et-3,5-chloroPh)₂DABMe₂. Synthetic Method A: ¹HNMR (CDCl₃, 300 MHz, rt) δ7.19 (s, 1, H_(aryl)), 2.64 (sextet, 4,J=7.19, CHH′CH₃), 2.36 (sextet, 4, J=7.11, CHH′CH₃), 2.10 (s, 6,N═C(Me)—C(Me)═N), 1.05 (t, 12, J=7.52, CH₂CH₃); ¹³C NMR (CDCl₃, 75 MHz,rt) δ168.8 (N═C—C═N), 149.3 (Ar: C_(ipso)), 132.3 and 127.4 (Ar: C_(o)and C_(m)), 124.7 (Ar: C_(p)), 22.5 (CH₂CH₃), 16.8 (N═C(Me)—C(Me)═N),12.1 (CH₂CH₃).

[1391] Nickel Polymerization Procedure: (0.06 mmol scale) Solid whitepolyethylene (14.6 g) was isolated.

[1392] Palladium Polymerization Procedure: (0.06 mmol scale)Polyethylene (0.06 g) was isolated as an oil. ¹H NMR spectrum (C₆D₆)shows branched polyethylene along with some internal olefinic endgroups.

[1393] Palladium Polymerization Procedure: {0.03 mmol scale; Isolated[(2,6-Et-3,5-chloroPh)₂DABMe₂)]PdMe(NCMe)]BAF was used.} Polyethylene(2.42 g) was isolated as an oil.

Example 415

[1394] α-Diimine is (2,6-Et-3-chloroPh)₂DABMe₂. Synthetic Method A: ¹HNMR (CDCl₃, 300 MHz, rt) δ7.10 (d, 2, J=8.43, H_(aryl)), 7.04 (d, 2,J=8.07, H_(aryl)), 2.65 (m, 2, CHH′CH₃), 2.49 (m, 2, CHH′CH₃), 2.30 (m,4, C′HH′C′H₃), 2.08 (s, 6, N═C(Me)—C(Me)═N), 1.15 and 1.07 (t, 6 each,J=7.52, CH₂CH₃ and C′H₂C′H₃); ¹³C NMR (CDCl₃, 75 MHz, rt) δ168.4(N═C—C═N), 148.5 (Ar: C_(ipso)), 132.0, 129.1 and 128.6 (Ar: C_(o),C_(o)′, C_(m)), 126.9 and 124.3 (Ar: C_(m)′ and C_(p)), 24.4 and 22.6(CH₂CH₃ and C′H₂C′H₃), 16.5 (N═C(Me)—C(Me)═N), 13.4 and 12.4 (CH₂CH₃ andC′H₂C′H₃).

[1395] Palladium Polymerization Procedure: {0.03 mmol scale; Isolated[(2,6-Et-3-chloroPh)₂DABMe₂)PdMe(NCMe)]BAF was used.} Polyethylene (˜1g) was isolated as an amorphous solid.

Example 416

[1396] α-Diimine is (2,6-bromo-4-MePh)₂DABMe₂. Synthetic Method A: ¹HNMR (CDCl₃, 300 MHz, rt) δ7.40 (m, 4, H_(aryl)), 2.32 (s, 6, Ar: Me),2.14 (s, 6, N═C(Me)—C(Me)═N); ¹³C NMR (CDCl₃, 75 MHz, rt) δ171.5(N═C—C═N), 144.9 (Ar: C_(ipso)), 135.7 (Ar: C_(p)), 132.4 (Ar: C_(m)),112.3 (Ar: C_(o)), 20.2 and 16.9 (N═C(Me)—C(Me)═N and Ar: Me)

[1397] Nickel Polymerization Procedure: (0.02 mmol scale) Solid whitepolyethylene (5.9 g) was isolated. ¹H NMR spectrum (C₆D₆) shows asignificant amount of branched polymer along with internal olefinic endgroups.

[1398] Palladium Polymerization Procedure: (0.06 mmol scale)Polyethylene (0.38 g) was isolated as an oil. ¹H NMR spectrum (C₆D₆)shows a significant amount of branched polymer along with internalolefinic end groups.

Example 417

[1399] α-Diimine is (2,6-Me-4-bromoPh)₂DABH₂. Synthetic Method A: ¹H NMR(CDCl₃, 300 MHz, rt) δ8.07 (s, 2, N═CH—CH═N), 7.24 (s, 4, H_(aryl)),2.15 (s, 12, Ar: Me); ¹³C NMR (CDCl₃, 300 MHz, rt) δ163.6 (N═C—C═N),148.7 (Ar: C_(ipso)), 131.0 and 128.7 (Ar: C_(o) and C_(m)), 117.7 (Ar:C_(p)), 18.1 (Ar: Me).

[1400] Nickel Polymerization Procedure: (0.06 mmol scale) Solid whitepolyethylene (9.5 g) was isolated.

[1401] Palladium Polymerization Procedure: (0.06 mmol scale) No polymerwas isolated, however, the ¹H NMR spectrum (C₆D₆) shows the productionof α- and internal olefins (butenes and higher olefins). A smallresonance exists at 1.3 ppm and is consistent with the resonance for(CH₂)_(n).

Example 418

[1402] α-Diimine is (2,6-Me-4-bromoPh)₂DABMe₂. Synthetic Method A: ¹HNMR (CDCl₃, 300 MHz, rt) δ7.22 (s, 4, H_(aryl)), 2.02 (s, 6,N═C(Me)—C(Me)═N), 2.00 (s, 12, Ar: Me); ¹³C NMR (CDCl₃, 75 MHz, rt)δ168.5 (N═C—C═N), 147.3 (Ar: C_(ipso)), 130.6 (Ar: C_(m)), 126.9 (Ar:C_(o)), 115.9 (Ar: C_(p)), 17.6 (Ar: Me), 15.9 (N═C(Me)—C(Me)═N).

[1403] Nickel Polymerization Procedure: (0.06 mmol scale) Solid whitepolyethylene (14.9 g) was isolated.

[1404] Palladium Polymerization Procedure: (0.06 mmol scale)Polyethylene (1.3 g) was isolated as an oil. The ¹H NMR spectrum (C₆D₆)shows resonances consistent with the formation of branched polymer.Resonances consistent with olefinic end groups are observed in thebaseline.

[1405] Palladium Polymerization Procedure: {0.03 mmol scale;Isolated[(2,6-Me-4-bromoPh)₂DABMe₂)PdMe(NCMe)]BAF was used.}Polyethylene (3.97 g) was isolated as a mixture of a soft white solidand an amorphous oil. ¹H NMR spectrum (C₆D₆) shows branchedpolyethylene.

Example 419

[1406] α-Diimine is (2-Me-6-chloroPh)₂DABMe₂.

[1407] Nickel Polymerization Procedure: (0.02 mmol scale) Solid whitepolyethylene (220 mg) was isolated. In addition, the ¹H NMR spectrum(C₆D₆) shows the production of 1- and 2-butenes.

[1408] Palladium Polymerization Procedure: (0.03 mmol scale; Isolated[(2-Me-6-chloroPh)₂DABMe₂]PdMe(NCMe)]SbF₆ was used.) Polyethylene (3.39g) was isolated as an oil. The ¹H NMR spectrum (C₆D₆) shows theproduction of branched polyethylene; internal olefin end groups are alsopresent.

Example 420 (2, 6-t-BuPh)₂DABAN

[1409] This compound was made by a procedure similar to that of Example25. Two g (9.74 mmol) of 2,5-di-t-butylaniline and 0.88 g (4.8 mmol) ofacenaphthenequinone were partially dissolved in 50 mL of methanol.Attempted crystallization from ether and from CH₂Cl₂ yielded anorange/yellow powder (1.75 g, 66% --not optimized). ¹H NMR (CDCl₃, 250MHz) δ7.85 (d, 2H, J=8.1Hz, BIAN: H_(p)), 7.44 (d, 2H, J=8.4 Hz, Ar:H_(m)), 7.33 (dd, 2H, J=8.4, 7.3 Hz, BIAN: H_(m)), 7.20 (dd, 2H, J=8.1,2.2 Hz, Ar: H_(p)), 6.99 (d, 2H, J=2.2 Hz, Ar: H_(o)), 6.86 (d, 2H,J=7.0 Hz, BIAN: H_(o)), 1.37, 1.27 (s, 18H each, C(CH₃)₃).

Example 421

[1410] A 100 mg sample of{[(2,6-i-PrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺BAF⁻ in a Schlenk flask wasdissolved in CH₂Cl₂ (4ml) and cyclopentene (8 ml) added. The flask wasflushed well with a 10% ethylene in N₂ mix and the solution stirred witha slow flow of the gas mixture passing through the flask. After 15 hoursthe product had solidified into a single mass of yellow/brown polymer.The reaction was quenched with MeOH and the polymer broken into piecesand washed with MeOH. Yield=2.0 g. DSC: Tm=165° C. (32J/g). Integrationof the ¹H-NMR spectrum indicated 83 mole % cyclopentene.

Example 422

[1411] A 37 mg sample of [(2,4,6-MePh)₂DABAn]NiBr₂ in cyclopentene (5ml) was placed in a Schlenk flask under an atmosphere of ethylene.Modified MAO (1.1 ml, 7.2 wt % Al) was added and the reaction allowed torun for 16 hours after which time the product had solidified into a massof green polymer. The reaction was quenched by addition of MeOH/10% HCland the polymer was crushed and washed well with MeOH and finally a 2%Irganox/acetone solution. Yield=3.6 g.

Example 423

[1412] A 30 mg sample of [(2,6-i-PrPh)₂DABMe₂]NiBr₂ was slurried intoluene (2 ml) and norbornene (2 g). PMAO (1ml, 9.6 wt % Al) was added.The solution immediately turned deep blue/black and in less than aminute became extremely viscous. The reaction was quenched after 15hours by addition of MeOH/10% HCl causing the polymer to precipitate.The solid was filtered, washed well with MeOH and finally with a 2%Irganox® 1010 in acetone solution. The polymer was cut into pieces anddried. Yield=0.8 g (40%). ¹H-NMR (ODCB, 120° C.): 1.0-2.5 ppm complexmultiplet confirms that the product is an addition polymer. The absenceof olefinic peaks precludes the existence of ROMP product and indicatesthat the polymer is not of extremely low molecular weight.

Example 424

[1413] A 32 mg sample of [(2,6-i-PrPh)₂DABMe₂]COCl₂ was slurried intoluene (2 ml) and norbornene (4 g). PMAO (1.5 ml, 9.6 wt % Al) wasadded. The solution immediately turned deep purple and within a fewminutes became extremely viscous and difficult to stir. The reaction wasquenched after 4 hours by addition of MeOH/10% HCl causing the polymerto precipitate. The solid was filtered, washed well with MeOH andfinally with a 2% Irganox in acetone solution. The polymer was driedovernight at 110° C. under vacuum. Yield=2.1 g (53%). It was possible tofurther purify the product by dissolving in cyclohexane andreprecipitating with MeOH. ¹H-NMR (TCE, 120° C.): 1.0-2.5 ppm complexmultiplet.

Example 425

[1414] A 33 mg sample of ((2,4,6-MePh)₂DABAn)COCl₂ was slurried intoluene (2 ml) and norbornene (4 g). PMAO (2.0 ml, 9.6 wt % Al) wasadded. The solution immediately turned deep blue and within a fewminutes the viscosity began to increase. The reaction was quenched after4 hours by addition of MeOH/10% HCl causing the polymer to precipitate.The solid was filtered, washed well with MeOH and finally with a 2%Irganox® 1010 in acetone solution. The polymer was dried overnight at110° C. under vacuum. Yield=0.8 g (13%). It was possible to furtherpurify the product by dissolving in cyclohexane and reprecipitating withMeOH. ¹H-NMR (TCE, 120° C.): 1.0-2.5 ppm complex multiplet.

Example 426

[1415] A 23 mg sample of [(2,4,6-MePh)₂DABH₂]PdMeCl was slurried intoluene (2 ml) and norbornene (2.7 g). PMAO (1.0 mL, 9.6 wt % Al) wasadded. Solids immediately formed and after a few seconds stirringstopped. The reaction was quenched after 2 hours by addition of MeOH/10%HCl. The solid was filtered, crushed and washed well with MeOH andfinally with a 2% Irganox® 1010 in acetone solution. Yield=2.5 g (92%).

Example 427

[1416] A 16 mg sample of [(2,4,6-MePh)₂DABH₂]NiBr₂ was slurried indicyclopentadiene (˜3 g). MMAO (1.2 ml, 7.2 wt % Al) was added. Solutionimmediately turned deep red/purple and started to foam. The reaction wasquenched after 16 hours by addition of MeOH/10% HCl which precipitatedthe polymer. The solid was filtered and washed well with MeOH andfinally with a 2% Irganox® 1010 in acetone solution. Yield=0.25 g.

Example 428

[1417] A 20 mg sample of [(2,4,6-MePh)₂DABH₂]PdMeCl was slurried intoluene (2 ml) and ethylidene norbornene (2 ml). PMAO (1.0 mL, 9.6 wt %Al) was added. The solution turned a pale orange and after an hour theviscosity had increased. After 14 hours the mixture had solidified intoa gel and stirring had stopped. The reaction was quenched by addition ofMeOH/10% HCl. The solid was filtered, crushed and washed well with MeOHand finally with a 2% Irganox® 1010 in acetone solution. Yield=0.7 g(39%).

Example 429

[1418] NiI₂ (0.26 g) was placed in THF (10 ml) and (2,6-i-PrPh)₂DABMe₂(340 mg) was added. The resulting mixture was stirred for 2 days afterwhich the THF was removed and pentane added. The red/brown solid wasisolated by filtration and washed several times with pentane. Yield=0.53g (89%).

[1419] A portion of the product (9 mg) in toluene (25 mL) in a Schlenkflask was placed under an atmosphere of ethylene (140 kPa [absolute])and 0.25 ml PMAO solution (9.6% Al) was added. The solution turned darkgreen and, after several hours at room temperature, became viscous.After 16 hours the reaction was quenched with MeOH/10% HCl whichprecipitated the polymer. The polymer (1.25 g) was collected byfiltration, washed well with MeOH and dried under reduced pressure. ¹HNMR indicated ˜133 methyl per 1000 methylene.

Example 430

[1420] CoI₂ (286 mg) was dissolved in THF (10 ml) and (2,6-iPrPh)₂DABMe₂(370 mg) was added. The resulting mixture was stirred for 3 days afterwhich the THF was removed and pentane added. The brown solid wasisolated by filtration and washed several times with pentane. Yield=0.29g (44%). ¹H NMR (THF-d₈) 1.0-1.4 (m, 24H, CH—CH₃), 2.06 (s, 6H,N═C—CH₃), 2.6-2.8 (m, 4H, C—CH—(CH₃)₂), 7.0-7.3 (m, 6H, aromatic). Thisdata is consistent with the formula: [(2,6-i-PrPh)₂DABMe₂]CoI₂

[1421] A portion of the above product (14 mg, 0.02 mmol) in toluene (25mL) in a Schlenk flask was placed under an atmosphere of ethylene (140kPa [absolute]) and 0.4 ml PMAO solution (9.6% Al) was added. Thesolution turned purple and, after several hours at room temperature,became viscous. After 18 hours the reaction was quenched with MeOH/10%HCl which precipitated the polymer. The polymer (634 mg) was collectedby filtration, washed well with MeOH and dried under reduced pressure.¹H NMR indicated ˜100 methyl per 1000 methylene. DSC: Tg=−45° C.

Example 431

[1422] Solid π-cyclooctenyl-1,5-cyclooctadienecobalt (I) (17 mg, 0.06mmol) (prepared according to: Gosser L., Inorg. Synth., 17, 112-15,1977) and solid (2,6-iPrPh)₂DABMe₂ (24 mg, 0.06 mmol) were placed in aSchlenk flask and toluene (25 mL) added. An ethylene atmosphere wasadmitted (34 kPa gauge) and the solution stirred for 5 minutes. Thefinal color was brown/green. 0.8 ml PMAO solution (9.6% Al) was added.After 18 hours the reaction was quenched with MeOH/10% HCl whichprecipitated the polymer. The polymer (190 mg) was collected byfiltration, washed well with MeOH and dried under reduced pressure. ¹HNMR indicated 90 methyl per 1000 methylene. DSC: Tg=−45° C.

Example 432

[1423] [(2,6-iPrPh)₂DABMe₂]COCl₂ (619 mg) was slurried in Et₂O (5 ml)and cooled to −25° C. Me₂Mg (63 mg in 5 ml Et₂O) was added and thesolution stirred for 15 minutes. Et₂O was removed under reduced pressureand the resulting bright purple solid was dissolved in pentane, filteredto remove MgCl₂ and the volume reduced to 5 ml. The solution was cooledto −25° C. for 2 days and the resulting purple crystals isolated byfiltration. Yield=420 mg (73%). Crystal structure determinationconfirmed that the product was [(2,6-iPrPh)₂DABMe₂]CoMe₂.

[1424] [(2,6-iPrPh)₂DABMe₂]CoMe₂ (34 mg) in toluene (25 mL) in a Schlenkflask was placed under an atmosphere of ethylene (140 kPa [absolute])and after stirring for 2 hours, 0.6 ml PMAO solution (9.6% Al) wasadded. The solution remained dark purple and, after several hours atroom temperature, became viscous. After 48 hours the reaction wasquenched with MeOH/10% HCl which precipitated the polymer. The polymer(0.838 g) was collected by filtration, washed well with MeOH and driedunder reduced pressure. Branching (¹H-NMR): 115 methyl per 1000methylene. DSC: Tg=−45° C.

Example 433

[1425] [(2,6-iPrPh)₂DABMe₂]CoMe₂ (30 mg) was dissolved in benzene (10 mlin a shaker tube) and the solution frozen. Montmorillionite K-10(Aldrich Chemical Co., Milwaukee, Wis., U.S.A.)(200 mg, conditioned at140° C. for 48 hrs under vacuum) suspended in benzene (10 ml) was addedon top of the frozen layer and frozen as well. The solution was thawedunder an ethylene atmosphere (6.9 MPa) and shaken at that pressure for18 hours. MeOH was added to the resulting polymer which was thenisolated by filtration, washed well with MeOH and dried under reducedpressure. Yield=7.5 g crystalline polyethylene. Branching (¹H-NMR): 18Methyl per 1000 methylene.

Example 434

[1426] [(2,6-iPrPh)₂DABMe₂]CoMe₂ (15 mg) was dissolved in benzene (10 mlin a shaker tube) and the solution frozen. Montmorillionite K-10 (100mg, conditioned at 600° C. for 48 hrs under vacuum) suspended in benzene(10 ml) was added on top of the frozen layer and frozen as well. Thesolution was thawed under an ethylene atmosphere (6.9 MPa) and shaken atthat pressure for 18 hours. MeOH was added to the resulting polymerwhich was then isolated by filtration, washed well with MeOH and driedunder reduced pressure. Yield=3 g polyethylene. Branching (¹H NMR): 11Methyl per 1000 methylene.

Example 435

[1427] [(2,6-iPrPh)₂DABMe₂]CoMe₂ (15 mg) was dissolved in benzene (10 mlin a shaker tube) and the solution frozen. Tris(pentaflorophenyl)boron(25 mg) dissolved in benzene (10 ml) was added on top of the frozenlayer and frozen as well. The solution was thawed under an ethyleneatmosphere (6.9 MPa) and shaken at that pressure for 18 hours. MeOH wasadded to the resulting polymer which was then isolated by filtration,washed well with MeOH and dried under reduced pressure. Yield=105 mgpolyethylene. Branching (¹H NMR): 60 Methyl per 1000 methylene.

Example 436

[1428] [(2,6-iPrPh)₂DABMe₂]CoMe₂ (15 mg) was dissolved in benzene (10 mlin a shaker tube) and the solution frozen. HBAF 2Et₂O (30 mg) slurriedin benzene (10 ml) was added on top of the frozen layer and frozen aswell. The solution was thawed under an ethylene atmosphere (6.9 MPa) andshaken at that pressure for 18 hours. MeOH was added to the resultingpolymer which was then isolated by filtration, washed well with MeOH anddried under reduced pressure. Yield=3.8 g polyethylene. Branching (¹HNMR): 21 Methyl per 1000 methylene.

Example 437

[1429] CoCl₂ (102 mg) was placed in acetonitrile and AgBF₄ (306 mg)added. The solution was stirred for 30 minutes after which the whiteAgCl was filtered off. (2,6-i-PrPh)₂DABMe₂ (318 mg) was added and thesolution stirred overnight. The acetonitrile was removed under reducedpressure and pentane added. The orange product was isolated byfiltration and washed and dried. ¹H-NMR (THF-d₈): 1.1-1.4 (m, C—CH—CH₃,24H), 1.8 (CH₃CN, 6H), 2.2 (N═C—CH₃, 6H), 2.7 (m, C—CH—CH_(3, 4)H),7.0-7.2 (m, C═CH, 6H). The spectrum is consistent with the molecularformula′. [((2,6-iprph)₂DABMe₂)Co(CH₃CN)₂](BF₄)₂

[1430] A portion of the product (43 mg) in toluene (25 mL) in a Schlenkflask was placed under an atmosphere of ethylene (35 kPa gauge) and 0.8ml PMAO solution (9.6% Al) was added. The solution turned dark purpleAfter 18 hours the reaction was quenched with MeOH/10% HCl whichprecipitated the polymer. The polymer (0.310 g) was collected byfiltration, washed well with MeOH and dried under reduced pressure.Branching (¹H NMR): 72 Methyl per 1000 methylene.

Example 438

[1431] Solid Co(II)[(CH₃)₂CHC(O)O⁻]₂ (17 mg, 0.073 mmol) and solid(2,6-iPrPh)₂DABMe₂ (32 mg, 0.079 mmol) were placed in a Schlenk flaskand toluene (25 mL) added. An ethylene atmosphere was admitted (140 kPa[absolute]) and 3.0 ml PMAO solution (9.6% Al) was added. After 18 hoursthe reaction was quenched with MeOH/10% HCl which precipitated thepolymer. The polymer (57 mg) was collected by filtration, washed wellwith MeOH and dried under reduced pressure. ¹H NMR indicated 32 methylper 1000 methylene.

Example 439

[1432] The complex {[(2,6-EtPh)₂DABMe₂]PdMe(NCMe)}⁺SbF₆ ^(D) was weighed(50 mg, 0.067 mmol) into a 100 mL round-bottom flask inside a dry box.Cyclopentene (20 mL, 3400 equivalents per Pd; unpurified) anddichloromethane (20 mL) were added to the flask, and stirred under anitrogen atmosphere to give a homogeneous solution. A precipitate hadformed after 2 days. After 7 days, the solvent was evaporated and thesolids were dried in a vacuum oven to give 0.39 g polymer (86turnovers/Pd). A sample of the polymer was washed several times withpetroleum ether and ether, then dried in a vacuum oven. The polymer waspressed at 290° C. into a transparent, gray-brown, tough film. DSC (0 to300° C., 10° C./min, first heat): T_(g)=120° C., T_(m) (onset toend)=179 to 232° C., heat of fusion=18 J/g. ¹H NMR (400 MHz, 120° C.,ortho-dichlorobenzene-d₄, referenced to solvent peak at 7.280 ppm):0.905 (bs, 1H, cis —CH—CH ₂—CH—), 1.321 (bs, 2H, cis —CH—CH ₂—CH ₂—CH—),1.724 and 1.764 (overlapping bs, 4H, trans —CH—CH ₂—CH ₂—CH— and—CH—CH₂—CH₂—CH—), 1.941 (bs, 1H, trans —CH—CH ₂—CH—). The ¹H NMRassignments are based upon 2D NMR correlation of the ¹H and ¹³C NMRchemical shifts, and are consistent with a poly(cis-1,3-cyclopentylene)repeat unit.

Example 440

[1433] The complex {[(2,6-iPrPh)₂DABAn]PdMe(OEt₂)}⁺SbF₆ ^(D) was weighed(50 mg, 0.054 mmol) into a 100 mL round-bottom flask inside a dry box.Cyclopentene (20 mL, 4200 equivalents per Pd; unpurified) anddichloromethane (20 mL) were added to the flask, and stirred under anitrogen atmosphere to give a homogeneous solution. A precipitate hadformed after 3 days. After 6 days, the solvents were evaporated and thesolids were dried in a vacuum oven to give 0.20 g polymer (55turnovers/Pd). A sample of the polymer was washed several times withpetroleum ether and ether, then dried in a vacuum oven. DSC (0 to 300°C., 10° C./min, first heat): T_(g)=42° C., T_(m) (onset to end)=183 to242° C., heat of fusion=18 J/g. ¹H NMR (400 MHz, 70° C., CDCl₃,referenced to solvent peak at 7.240 ppm): 0.75 (bm, 1H, cis —CH—CH₂—CH—), 1.20 (bs, 2H, cis —CH—CH ₂—CH ₂—CH—), 1.59 and 1.68 (overlappingbs, 4H, trans —CH—CH ₂—CH ₂—CH— and —CH—CH₂—CH₂—CH—), 1.83 (bs, 1H,trans —CH—CH ₂—CH—). The ¹H NMR assignments are based upon 2D NMRcorrelation of the ¹H and ¹³C NMR chemical shifts, and are consistentwith a poly(cis-1,3-cyclopentylene) repeat unit.

Example 441

[1434] The complex [(2,6-iPrPh)₂DABMe₂]PdMeCl was added (28 mg, 0.050mmol) to a glass vial containing cyclopentene (3.40 g, 1000 equivalentsper Pd; distilled twice from Na) inside a dry box. A solution of MMAO inheptane (1.47 mL, 1.7 M Al, 50 equivalents per Pd) was added withstirring to give a homogeneous solution. A precipitate began to formimmediately. After 2 days, the solids were collected by vacuumfiltration, washed several times on the filter with petroleum ether andether, then dried in a vacuum oven to give 0.254 g polymer (75turnovers/Pd). The polymer was pressed at 250° C. into a transparent,gray-brown, tough film. DSC (0 to 300° C., 10° C./min, first heat)T_(g)=114° C., T_(m) (onset to end)=193 to 240° C., heat of fusion=14J/g. GPC (Dissolved in 1,2,4-trichlorobenzene at 150° C., run intetrachloroethylene at 100° C., polystyrene calibration): peakMW=154,000, M_(n)=70,200, M_(w)=171,000, M_(w)/M_(n)=2.43.

Example 442

[1435] The complex {[(2,6-iPrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺ SbF₆ ^(D)was weighed (42 mg, 0.050 mmol) into a glass vial inside a dry box.Cyclopentene (3.40 g, 1000 equivalents per Pd; distilled twice from Na)and dichloromethane (4.4 mL) were added with stirring to give ahomogeneous solution. After 1 day, the solids were collected by vacuumfiltration, washed several times on the filter with petroleum ether andether, then dried in a vacuum oven to give 1.605 g polymer (471turnovers/Pd). The polymer was pressed at 250° C. into a transparent,gray-brown, tough film. TGA (25 to 600° C., 10° C./min, nitrogen): T_(d)(onset to end)=473 to 499, 97.06% weight loss. TGA (25 to 600° C., 10°C./min, air): T_(d)=350° C., 5% weight loss. DSC (0 to 300° C., 10°C./min, second heat): T_(g)=94° C., T_(m) (onset to end)=191 to 242° C.,heat of fusion=14 J/g. GPC (Dissolved in 1,2,4-trichlorobenzene at 150°C., run in tetrachloroethylene at 100° C., polystyrene calibration):peak MW=152,000, M_(n)=76,000, M_(w)=136,000, M_(w)/M_(n)=1.79.

Example 443

[1436] The complex [(2,6-iPrPh)₂DABMe₂]PdCl₂ was weighed (29 mg, 0.050mmol) into a glass vial inside a dry box. Cyclopentene was added (6.81g, 2000 equivalents per Pd; distilled from polyphosphoric acid), and thevial was cooled to <0° C. A solution of MMAO in heptane (1.00 mL, 1.7 MAl, 34 equivalents per Pd) was added with stirring to give a homogeneoussolution. After 1 day, a copious precipitate had formed. After 2 days,the solids were collected by vacuum filtration, washed several times onthe filter with ether and cyclohexane, then dried in a vacuum oven togive 1.774 g polymer (520 turnovers/Pd). The polymer was coated with5000 ppm Irganox® 1010 by evaporating an acetone slurry and drying in avacuum oven. The polymer was pressed at 290° C. into a transparent,gray-brown, tough film. DSC (25 to 330° C., 10° C./min, second heat):T_(g)=105° C., T_(m) (onset to end)=163 to 244° C., heat of fusion=21J/g.

Example 444

[1437] The complex [(2,6-iPrPh)₂DABMe₂]PdCl₂ was weighed (29 mg, 0.050mmol) into a glass vial inside a dry box. Cyclopentene was added (6.81g, 2000 equivalents per Pd; distilled from polyphosphoric acid), and thevial was cooled to <0° C. A solution of EtAlCl₂ in hexane (1.7 mL, 1.0M, 34 equivalents per Pd) was added with stirring to give a homogeneoussolution. After 4 days, the solids were collected by vacuum filtration,washed several times on the filter with ether and cyclohexane, thendried in a vacuum oven to give 1.427 g polymer (419 turnovers/Pd). Thepolymer was coated with 5000 ppm Irganox® 1010 by evaporating an acetoneslurry and drying in a vacuum oven. The polymer was pressed at 290° C.into a transparent, gray-brown, tough film. DSC (25 to 330° C., 10°C./min, second heat): T_(g)=103° C., T_(m) (onset to end)=153 to 256°C., heat of fusion=23 J/g.

Example 445

[1438] The complex [(2,6-iPrPh)₂DABMe₂]PdCl₂ was weighed (29 mg, 0.050mmol) into a glass vial inside a dry box. Cyclopentene was added (6.81g, 2000 equivalents per Pd; distilled from polyphosphoric acid), and thevial was cooled to <0° C. A solution of EtAlCl₂áEt₂AlCl in toluene (1.9mL, 0.91 M, 68 equivalents Al per Pd) was added with stirring to give ahomogeneous solution. After 4 days, the solids were collected by vacuumfiltration, washed several times on the filter with ether andcyclohexane, then dried in a vacuum oven to give 1.460 g polymer (429turnovers/Pd). The polymer was coated with 5000 ppm Irganox® 1010 byevaporating an acetone slurry and drying in a vacuum oven. The polymerwas pressed at 290° C. into a transparent, gray-brown, tough film. DSC(25 to 330° C., 10° C./min, second heat): T_(g)=101° C., T_(m) (onset toend)=161 to 258° C., heat of fusion=22 J/g.

Example 446

[1439] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed (32 mg, 0.050mmol) into a glass vial inside a dry box. Cyclopentene was added (6.81g, 2000 equivalents per Ni; treated with 5 A molecular sieves, anddistilled from Na and Ph₃CH), and the vial was cooled to <0° C. Asolution of EtAlCl₂áEt₂AlCl in toluene (1.9 mL, 0.91 M, 68 equivalentsAl per Ni) was added with stirring to give a homogeneous solution. After5 days, the solids were collected by vacuum filtration, washed severaltimes on the filter with ether and cyclohexane, and dried in a vacuumoven to give 2.421 g polymer (711 turnovers/Ni). The polymer was coatedwith 5000 ppm Irganox® 1010 by evaporating an acetone slurry and dryingin a vacuum oven. The polymer was pressed at 290° C. into a transparent,brown, tough film. DSC (25 to 330° C., 10° C./min, second heat):T_(g)=103° C., T_(m) (onset to end)=178 to 272° C., heat of fusion=22J/g.

Example 447

[1440] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed (128 mg, 0.202mmol) into a glass bottle inside a dry box. Cyclopentene was added (27.1g, 2000 equivalents per Ni; treated with polyphosphoric acid, anddistilled from Na). A solution of EtAlCl₂ in hexane (6.8 mL, 1.0 M, 34equivalents Al per Ni) was added with stirring to give a homogeneoussolution. After 1 day, additional cyclopentene was added (58 g, 6200total equivalents per Ni) to the bottle containing a heavy slurry. After5 days, the solids were slurried with ether, collected by vacuumfiltration, washed several times with ether and cyclohexane on thefilter, and dried in a vacuum oven to give 36.584 g polymer (2660turnovers/Ni). The polymer was washed with 50:50 aqueous HCl/MeOH,followed by several washings with 50:50H₂0/MeOH, and dried in a vacuumoven. A fine powder sample was obtained using a 60 mesh screen, andcoated with 5000 ppm Irganox® 1010 by evaporating an acetone slurry anddrying in a vacuum oven. The fine powder was pressed at 290° C. into atransparent, pale brown, tough film. TGA (25 to 700° C., 10° C./min,nitrogen) T_(d) (onset to end)=478 to 510° C., 99.28% weight loss. DSC(25 to 330° C., 10° C./min, second heat): T_(g)=101° C., T_(m) (onset toend)=174 to 279° C., heat of fusion=25 J/g. DSC (330 to 25° C., 10°C./min, first cool): T_(c) (onset to end)=247 to 142° C., heat offusion=28 J/g; T_(c) (peak)=223° C. DSC isothermal crystallizations wereperformed by heating samples to 330° C. followed by rapid cooling to thespecified temperatures, ° C., and measuring the exotherm half-times(min): 200 (1.55), 210 (1.57), 220 (1.43), 225 (<1.4), 230 (1.45), 240(1.88), 245 (1.62). DSC thermal fractionation was performed by heating asample to 330° C. followed by stepwise isothermal equilibration at thespecified temperatures, ° C., and times (hr): 290 (10), 280 (10), 270(10), 260 (10), 250 (10), 240 (8), 230 (8), 220 (8), 210 (8), 200 (6),190 (6), 180 (6), 170 (6), 160 (4), 150 (4), 140 (4), 130 (3), 120 (3),110 (3). DSC (25 to 330° C., 10;C/min, thermal fractionation sample):T_(g)=100° C.; T_(m), ° C. (heat of fusion, J/g)=128 (0.4), 139 (0.8),146 (1.1), 156 (1.5), 166 (1.9), 176 (2.1), 187 (2.6), 197 (3.0), 207(3.2), 216 (3.2), 226 (3.4), 237 (3.6), 248 (3.7), 258 (2.3), 269 (1.2),279 (0.5), 283 (0.1); total heat of fusion=34.6 J/g. DMA (−100 to 200°C., 1, 2, 3, 5, 10 Hz; pressed film): modulus (−100° C.)=2500 MPa, γrelaxation=−67 to −70° C. (activation energy=11 kcal/mol), modulus (25°C.)=1600 MPa, α relaxation (T_(g))=109 to 110° C. (activation energy=139kcal/mol).

Example 448

[1441] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed (32 mg, 0.050mmol) into a glass bottle inside a dry box. Cyclopentene was added (34.1g, 10,000 equivalents per Ni; high-purity synthetic material distilledfrom Na), and the vial was cooled to <0° C. A solution of MMAO inheptane (2.7 mL, 1.95 M Al, 100 equivalents Al per Ni) was added withstirring to give a homogeneous solution. After 3 days, a copiousprecipitate had formed. After 7 days, the reaction was quenched with 20mL MeOH and 2 mL acetylacetone. The solids were washed several timeswith 3 mL aqueous HCl in 30 mL MeOH by decanting the free liquids. Thesolids were collected by vacuum filtration, washed several times on thefilter with methanol, and dried in a vacuum oven to give 14.365 gpolymer (4200 turnovers/Ni). The polymer was coated with 5000 ppmIrganox® 1010 by evaporating an acetone slurry and drying in a vacuumoven. The polymer was pressed at 290° C. into a transparent, colorless,tough film. DSC (0 to 320° C., 20° C./min, second heat): T_(g)=95° C.,T_(m) (onset to end)=175 to 287° C., heat of fusion=20 J/g.

Example 449

[1442] The complex [(2,4,6-MePh)₂DABAn]NiBr₂ was weighed (32 mg, 0.050mmol) into a glass bottle inside a dry box. Cyclopentene was added (34.1g, 10,000 equivalents per Ni; high-purity synthetic material distilledfrom Na), and the vial was cooled to <0° C. A solution ofEtAlCl₂áEt₂AlCl in toluene (2.8 mL, 0.91 M, 100 equivalents Al per Ni)was added with stirring to give a homogeneous solution. After 3 days, aprecipitate had formed. After 7 days, the reaction was quenched with 20mL MeOH and 2 mL acetylacetone. The solids were washed several timeswith 3 mL aqueous HCl in 30 mL MeOH by decanting the free liquids. Thesolids were collected by vacuum filtration, washed several times on thefilter with methanol, and dried in a vacuum oven to give 7.254 g polymer(2113 turnovers/Ni). The polymer was coated with 5000 ppm Irganox® 1010by evaporating an acetone slurry and drying in a vacuum oven. Thepolymer was pressed at 290° C. into a transparent, colorless, toughfilm. DSC (0 to 320° C., 20° C./min, second heat): T_(g)=94° C., T_(m)(onset to end)=189 to 274° C., heat of fusion=18 J/g.

Example 450

[1443] Bis(benzonitrile)palladium dichloride (0.385 g, 1.00 mmol) and(2,6-iPrPh)₂DABMe₂ (0.405 g, 1.00 mmol) were weighed into a glass vialinside a dry box. Dichloromethane (8 mL) was added to give a dark orangesolution. Upon standing, the solution gradually lightened in color.Cyclohexane was added to precipitate an orange solid. The solids werecollected by vacuum filtration, washed several times with cyclohexane,and dried under vacuum to give 0.463 g (80%) of the complex[(2,6-iPrPh)₂DABMe₂]PdCl₂. ¹H NMR (300 MHz, CD₂Cl₂, referenced tosolvent peak at 5.32 ppm): 1.19 (d, 12H, CH ₃—CHAr—CH₃), 1.45 (d, 12H,CH₃—CHAr—CH ₃), 2.07 (s, 6H, (CH ₃—C═N—Ar), 3.07 (m, 4H, (CH₃)₂—CH—Ar),7.27 (d, 4H, meta ArH), 7.38 (t, 2H, para ArH).

Example 451

[1444] A sample of polycyclopentene prepared in a similar fashion toExample 317 gave a transparent, brown, tough film when pressed at 290°C. DSC (25 to 330° C., 10° C./min, second heat): T_(g)=98° C., T_(m)(onset to end)=174 to 284° C., heat of fusion=26 J/g. A 5 g sample thatwas molded at 280° C. into a test specimen suitable for an apparatusthat measures the response to changes in pressure, volume andtemperature, and the data output was used to calculate the followingphysical properties. Specific gravity, g/cm³, at temperature (° C.):1.033 (30) , 1.010 (110° C.) , 0.887 (280), 0.853 (350). Bulkcompression modulus, MPa, at temperature (° C.): 3500 (30), 2300 (110),1500 (170). The coefficient of linear thermal expansion was 0.00009 °C.^(D1) between 30 and 110° C.

Example 452

[1445] A solution of {[(2,6-iPrPh)₂DABMe₂]PdCH₂CH₂CH₂C(O)OCH₃}⁺SbF₆ ⁻(1.703 g) in 1.5 L CH₂Cl₂ was transferred under nitrogen to a nitrogenpurged 1 gallon Hastalloy® autoclave. The autoclave was charged with 300g of propylene and stirred for 24 h while maintaining the temperature at25° C. The pressure was then vented. The polymer product was floating onthe solvent. Most of the solvent was removed in vacuo, and the polymerwas dissolved in minimal CHCl₃ and then reprecipitated by addition ofexcess acetone. The polymer was dried in vacuo at 60° C. for three daysto give 271 g of green rubber. Quantitative ¹³C NMR analysis, branchingper 1000 CH₂: Total methyls (365), ≧Butyl and end of chains (8),CHCH₂CH(CH₃)₂ (31), —(CH₂)_(n)CH(CH₃)₂ n≧2 (25). Based on the totalmethyls, the fraction of 1,3-enchainment is 38%. Analysis of backbonecarbons (per 1000 CH₂): δ⁺ (138), δ⁺/γ (1.36).

[1446] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity47.1728 14.6401 46.7692 9.89618 46.3285 13.3791 45.8719 7.94399 45.468411.1421 45.2719 7.80142 44.4754 7.11855 39.1923 29.1488 38.2791 14.214238.1304 18.7602 37.9074 14.9366 37.6631 15.0761 37.2809 39.5816 35.50748.29039 34.865 9.75536 34.5889 14.9541 34.2915 24.0579 33.2455 9.8679732.9747 19.2516 30.6013 52.6926 30.134 55.0735 γ 30.0066 25.1831 γ29.7518 144.066 δ⁺ 29.3217 12.2121 3B₄ 28.2013 51.5842 27.9783 39.556627.5376 33.189 27.373 35.5457 27.1659 47.0796 27.0438 42.1247 25.631521.6632 terminal methine of XXVIII 23.3589 15.3063 Methyl of XXVIII andXXIX, 2B₄, 2B₅+, 2EOC 23.0722 18.4837 Methyl of XXVIII and XXIX, 2B₄,2B₅+, 2EOC 22.5306 77.0243 Methyl of XXVIII and XXIX, 2B₄, 2B₅+, 2EOC21.1129 7.78367 20.5554 26.9634 1B₁ 20.4386 30.3105 1B₁ 20.0085 22.4781B₁ 19.743 46.6467 1B₁ 13.8812 9.03898 1B₄+, 1EOC

Example 453

[1447] A 250 mL Schlenk flask was charged with 10 mg of[(2,6-i-PrPh)₂DABH₂]NiBr₂ (1.7×10⁻⁵ mol), and 75 mL of dry toluene. Theflask was cooled to 0° C. and filled with propylene (1 atm) beforeaddition of 1.5 mL of a 10% MAO solution in toluene. After 45 min,acetone and water were added to quench the reaction. Solid polypropylenewas recovered from the flask and washed with 6 M HCl, H₂O, and acetone.The resulting polymer was dried under high vacuum overnight to yield 1.2g (2300 TO/h) polypropylene. Differential scanning calorimetry: Tg=−19°C. GPC (trichlorobenzene, 135° C., polystyrene reference): Mn=32,500;Mw=60,600; Mw/Mn=1.86. Quantitative ¹³C NMR analysis, branching per 1000CH₂: Total methyls (813), Based on the total methyls, the fraction of1,3-enchainment is 7%. Analysis of backbone carbons (per 1000 CH₂): δ⁺(3), δ⁺/γ (0.4).

[1448] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity47.194 18.27 46.9922 21.3352 46.8276 35.7365 46.2011 27.2778 45.41538.55108 43.5356 2.71929 42.925 3.37998 41.5551 2.63256 38.826 3.0389938.4012 10.2858 38.0561 8.50185 37.626 7.10732 37.4879 6.55335 37.27559.25058 36.1021 4.48005 35.3057 14.5319 34.4986 11.1193 33.219 9.4354832.9375 4.94953 32.242 3.16177 30.8349 24.1766 30.5217 19.8151 30.09163.70031 28.1111 144 27.5217 13.9133 27.1394 3.83857 24.5005 6.9494621.0439 5.25857 20.5342 40.8641 20.0191 60.4325 19.8758 63.0429 16.92366.47935 16.3926 5.92056 14.9006 10.6275 14.513 3.39891

Example 454

[1449] Preparation of (2-t-BuPh)₂DABAn. A Schlenk tube was charged with2-t-butylaniline (3.00 mL, 19.2 mmol) and acenaphthenequinone (1.71 g,9.39 mmol). The reagents were partially dissolved in 50 mL of methanol(acenaphthenequinone was not completely soluble) and 1-2 mL of formicacid was added. An orange solid formed and was collected via filtrationafter stirring overnight. The solid was crystallized from CH₂Cl₂ (3.51g, 84.1%). ¹H NMR (CDCl₃, 250 MHz) δ7.85 (d, 2H, J=8.0 Hz, BIAn: H_(p)),7.52 (m, 2H, Ar: H_(m)), 7.35 (dd, 2H, J=8.0, 7.3 Hz, BIAn: H_(m)), 7.21(m, 4H, Ar: H_(m) and H_(p)), 6.92 (m, 2H, Ar: H_(o)), 6.81 (d, 2H,J=6.9 Hz, BIAn: H_(o)), 1.38 (s, 18H, C(CH₃)₃).

Example 455

[1450] Preparation of (2,5-t-BuPh)₂DABAn. A Schlenk tube was chargedwith 2,5-di-t-butylaniline (2.00 g, 9.74 mmol) and acenaphthenequinone(0.88 g, 4.8 mmol). The reagents were partially dissolved in 50 mL ofmethanol (acenaphthenequinone was not completely soluble) and 1-2 mL offormic acid was added. A solid was collected via filtration afterstirring overnight. Attempted crystallization from ether and from CH₂Cl₂yielded an orange/yellow powder (1.75 g, 66%. ¹H NMR (CDCl₃, 250 MHz)δ7.85 (d, 2H, J=8.1 Hz, BIAn: H_(p)), 7.44 (d, 2H, J=8.4 Hz, Ar: H_(m)),7.33 (dd, 2H, J=8.4, 7.3 Hz, BIAn: H_(m)), 7.20 (dd, 2H, J=8.1, 2.2 Hz,Ar: H_(p)), 6.99 (d, 2H, J=2.2 Hz, Ar: H_(o)), 6.86 (d, 2H, J=7.0 Hz,BIAn: H_(o)), 1.37, 1.27 (s, 18H each, C(CH₃)₃).

Example 456

[1451] Preparation of [(2-t-BuPh)₂DABAn]NiBr₂. A Schlenk tube wascharged with 0.202 g (0.454 mmol) of (2-t-BuPh)₂DABAn, which was thendissolved in 15 mL of CH₂Cl₂. This solution was cannulated onto asuspension of (DME)NiBr₂ (0.135 g, 0.437 mmol) in 10 mL of CH₂Cl₂. Thereaction mixture was allowed to stir overnight resulting in a deep redsolution. The solution was filtered and the solvent evaporated undervacuum. The residue was washed with ether (2×10 mL) and an orange/rustsolid was isolated and dried under vacuum (0.18 g, 62%).

Example 457

[1452] Preparation of [(2,5-t-BuPh)₂DABAn]NiBr₂. A Schlenk tube wascharged with 0.559 g (1.00 mmol) of (2,5-t-BuPh)₂DABAn, 0.310 g (1.00mmol) of (DME)NiBr₂ and 35 mL of CH₂Cl₂. The reaction mixture wasallowed to stir overnight. The solution was filtered and the solventevaporated under vacuum. The residue was washed with ether and resultedin an orange solid which was dried under vacuum (0.64 g, 83%).

Example 458

[1453] Preparation of highly chain-straightened polypropylene with a lowTg. The complex [(2-t-BuPh)₂DABAn]NiBr₂ (0.0133 g, 2.0×10⁻⁵ mol) wasplaced into a flame-dried 250 mL Schlenk flask which was then evacuatedand back-filled with propylene. Freshly distilled toluene (100 mL) wasadded via syringe and the resulting solution was stirred in a water bathat room temperature. Polymerization was initiated by addition ofmethylaluminoxane (MAO; 1.5 mL 10% soln in toluene) and a propyleneatmosphere was maintained throughout the course of the reaction. Thereaction mixture was stirred for two hours at constant temperaturefollowed by quenching with 6M HCl. Polymer was precipitated from theresulting solution with acetone, collected, washed with water andacetone, and dried under vacuum. Yield=1.41 g. DSC: T_(g) −53.6° C.,T_(m) −20.4° C. (apparent Tm is a small shoulder on the Tg).Quantitative ¹³C NMR analysis, branching per 1000 CH₂: Total methyls(226), ≧Butyl and end of chains (8.5), CHCH₂CH(CH₃)₂ (2.3),—(CH₂)_(n)CH(CH₃)₂ n≧2 (12.1). Based on the total methyls, the fractionof 1,3-enchainment is 53%. Analysis of backbone carbons (per 1000 CH₂):δ⁺ (254), δ⁺/γ (1.96).

Example 459

[1454] Preparation of highly chain-straightened polypropylene with a lowTg. The complex [(2,5-t-BuPh)₂DABAn]NiBr₂ (0.0155 g, 2.0×10⁻⁵ mol) wasplaced into a flame-dried 250 mL Schlenk flask which was then evacuatedand back-filled with propylene. Freshly distilled toluene (100 mL) wasadded via syringe and the resulting solution was stirred in a water bathat room temperature. Polymerization was initiated by addition of 1.5 mLof a 10% MAO solution in toluene, and a propylene atmosphere wasmaintained throughout the course of the reaction. The reaction mixturewas stirred for two hours at constant temperature followed by quenchingwith 6M HCl. Polymer was precipitated from the resulting solution withacetone, collected, washed with water and acetone, and dried undervacuum. Yield=0.75 g. DSC: T_(g) −53.0° C., T_(m) none observed.Quantitative ¹³C NMR analysis, branching per 1000 CH₂: Total methyls(307), ≧Butyl and end of chains (11.2), —CHCH₂CH(CH₃)₂ (11 . 5)—(CH₂)_(n)CH(CH₃)₂, n≧2 (5. 9). Based on the total methyls, the fractionof 1,3-enchainment is 43%.

[1455] Listed below are the ¹³C NMR data upon which the above analysisis based. ¹³C NMR data TCB, 120 C., 0.05M CrAcAc Freq ppm Intensity46.3126 6.77995 46.079 6.56802 45.463 7.82411 45.2453 6.98049 39.17648.95757 38.4384 5.42739 38.1145 20.5702 37.8755 18.8654 37.626 19.291737.2702 128.202 35.0773 6.30042 34.5304 19.5098 34.2543 38.6071 33.78184.3205 33.2986 16.3395 32.9588 72.1002 31.934 10.626 31.419 5.5712430.5907 41.727 30.1287 134.312 γ 29.7518 351.463 δ⁺ 29.3217 9.5897128.1589 21.1043 27.9677 17.7659 27.5589 44.1485 27.3783 25.0491 27.1766119.562 27.0226 52.4586 ˜25.6 terminal methine of XXVIII 24.5908 8.6946224.4315 9.27804 22.5253 30.7474 region of methyls of XXVIII and XXIX,2B₄+, 2EOC 20.4333 20.0121 1B₁ 19.7271 103.079 1B₁ 14.7679 5.002214.4068 4.56246 13.8812 12.3077 1B₄+, 1EOC

Example 460

[1456] Preparation of highly chain-straightened poly-1-hexene with ahigh T_(m). A flame-dried 250 mL Schlenk flask under a nitrogenatmosphere was charged with 40 mL of freshly distilled toluene, 0.0133 gof [(2-t-BuPh)₂DABAn]NiBr₂ (2.0×10⁻⁵ mol), 5.0 mL of 1-hexene, and 55 mLmore toluene (100 mL total volume of liquid). Polymerization wasinitiated by addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for 11.5 hours at room temperature followedby quenching with 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=1.84 g. DSC: T_(g) −44.8° C.,T_(m) 46.0° C.

Example 461

[1457] Preparation of highly chain-straightened poly-1-hexene with ahigh T_(m). A flame-dried 250 mL Schlenk flask under a nitrogenatmosphere was charged with 40 mL of freshly distilled toluene, 0.0155 gof [(2,5-t-BuPh)₂DABAn]NiBr₂ (2.0×10⁻⁵ mol), 5.0 mL of 1-hexene, and 55mL more toluene (100 mL total volume of liquid). Polymerization wasinitiated by addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for 11.5 hours at room temperature followedby quenching with 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=1.07 g. DSC: T_(g) −54.7° C.,T_(m) 12.5° C.

Example 462

[1458] Preparation of [(2-t-BuPh)₂DABAn]PdMe₂ from(1,5-cyclooctadiene)PdMe₂. The Pd(II) precursor(1,5-cyclooctadiene)PdMe₂ ((COD)PdMe₂) was prepared according reportedprocedures (Rudler-Chauvin, M.; Rudler, H. J. Organomet. Chem., 1977,134, 115.) and was handled using Schlenk techniques at temperatures of−10° C. or below. A flame-dried Schlenk tube was charged with 0.056 g(0.229 mmol) of (COD)PdMe₂ and cooled to −40° C. in a dryice/isopropanol bath. The solid was dissolved in 10 mL of ether, and thediimine (2-t-BuPh)₂DABAn (0.106 g, 0.238 mmol) was cannulated onto thestirring solution as a slurry in 15 mL of ether. The reaction was warmedto 0°) C. and stirring was continued for two hours. The reaction flaskwas stored at −30° C. for several days and resulted in the formation ofa green precipitate which was isolated via filtration. The supernatantwas pumped dry under high vacuum and also resulted in a green solid.Both solids were determined to be [(2-t-BuPh)₂DABAn]PdMe₂ by ¹H NMRspectroscopy. Isolated yield=0.083 g (0.143 mmol, 62.4%).

Example 463

[1459] Preparation of [(2,5-t-BuPh)₂DABAn]PdMe₂ from(1,5-cyclooctadiene)PdMe₂. The Pd(II) precursor(1,5-cyclooctadiene)PdMe₂ ((COD)PdMe₂) was prepared according reportedprocedures (Rudler-Chauvin, M.; Rudler, H. J. Organomet. Chem., 1977,134, 115.) and was handled using Schlenk techniques at temperatures of−10° C. or below. A flame-dried Schlenk tube was charged with 0.102 g(0.417 mmol) of (COD)PdMe₂ and cooled to −30° C. in a dryice/isopropanol bath. The solid was dissolved in 10 mL of ether, and thediimine (2,5-t-BuPh)₂DABAn (0.234 g, 0.420 mmol) was cannulated onto thestirring solution as a slurry in 40 mL of ether. The reaction was warmedto 0° C. and stirring was continued for four hours. The reaction flaskwas stored at −30° C. overnight. The resulting dark green solution wasfiltered and the solvent was pulled off under high vacuum to give a darkgreen powder. Analysis by ¹H NMR spectroscopy showed the solid to beconsistent with the desired product, [(2,5-t-BuPh)₂DABAn]PdMe₂.Yield=0.256 g (0.370 mmol, 88.7%).

Example 464

[1460] In a dry box, polymer from Example 469 (0.57 g), THF (10.10 g)and acetic anhydride (0.65 g) were placed in a 20 mL vial equipped witha stirring bar. After one hour at room temperature, the vial was removedfrom the dry box and the polymerization terminated by the addition ofTHF, water and ether. The organic phase was separated, washed with water(2×), dried over anhydrous sodium sulfate, concentrated at reducedpressure and then dried under vacuum, affording 4.44 g of polymer. GPCanalysis (PS STD.): Mn=17600, Mw=26000, PD=1.48.

Example 465 Preparation of CH₂═CH(CH₂)₂CHICH₂(CF₂)₂OCF₂CF₂SO₂F

[1461] A mixture of 72 g of hexadiene, 127.8 g of ICF₂CF₂OCF₂CF₂SO₂F,7.0 g of Cu powder and 180 mL of hexane was stirred at 90° C. overnight.Solids were removed by filtration and washed with hexane. After removalof volatiles, residue was distilled to give 115.3 g of product, bp 80°C./210 Pa. ¹⁹F NMR: +45 (t, J=6.0 Hz, 1F), −82.7 (m, 2F), −88.1 (dt,J=42.5 Hz, J=12.6 Hz, 1F), −88.7 (dt, J=45.5 Hz, J=12.6 Hz, 1F), −112.7(m, 2F), −115.9 (ddd, J=2662.2 Hz, J=30.0 Hz, J=8.2 Hz, 1F), −118.9(ddd, J=262.2 Hz, J=26.8 Hz, J=7.4 Hz, 1F).

Example 466 Preparation of CH₂═CH(CH₂)₄ (CF₂)₂OCF₂CF₂SO₂F

[1462] To a stirred solution of 100 g ofCH₂═CH(CH₂)₂CHICH₂(CF₂)₂OCF₂CF₂SO₂F and 200 mL of ether was added 63 gof Bu₃SnH at room temperature. After the addition was complete, thereaction mixture was refluxed for 4 hours and then cooled with icewater. Excess of Bu₃SnH was destroyed by addition of iodine. After beingdiluted with 200 mL of ether, the reaction mixture was treated with asolution of 25 g of KF in 200 mL of water for 30 min. The solids wereremoved by filtration through a funnel with silica gel and washed withether. The ether layer was separated and washed with water, aqueous NaClsolution and dried over MgSO₄. After removal of the ether, residue wasdistilled to give 54.7 g of product, bp 72° C./1.3 kPa, and 12.2 g ofstarting material.

[1463]¹⁹F NMR: +45 (m, 1F), −82.7 (m, 2F), −88.0 (m, 2F), −112.6 (m,2F), −118.6 (t, J=18.4 Hz, 2F).

Example 467 Preparation of CH₂═CH(CH₂)₄(CF₂)₄OCF₂CF₂SO₂F

[1464] A mixture of 24 g of hexadiene, 53 g of I(CF₂)₄OCF₂CF₂SO₂F, 3.0 gof Cu powder and 60 mL of hexane was stirred at 70° C. overnight. Solidswere removed by filtration and washed with hexane. After removal ofvolatiles, residue was distilled to give 115.3 g of adduct,CH₂═CH(CH₂)₂CHICH₂(CF₂)₄OCF₂CF₂SO₂F, bp 74° C./9 Pa. ¹⁹F NMR: +45.5 (m,1F), −82.4 (m, 2F), −83.5 (m, 2F), −112.2 (dm, J=270 Hz, 1F), −112.6 (m,2F), −115.2 (dm, J=270 Hz, 1F), −124.3 (s, 2F), −125.5 (m, 2F).

[1465] To stirred solution of 47 g ofCH₂═CH(CH₂)₂CHICH₂(CF₂)₄OCF₂CF₂SO₂F and 150 mL of ether was added 27 gof Bu₃SnH at room temperature. After the addition was complete, thereaction mixture was stirred overnight. Excess of Bu₃SnH was destroyedby addition of iodine. After being diluted with 150 mL of ether, thereaction mixture was treated with a solution of 20 g of KF in 100 mL ofwater for 30 min. The solids were removed by filtration through a funnelwith silica gel and washed with ether. The ether layer was separated andwashed with water, aqueous NaCl solution and dried over MgSO₄. Afterremoval of the ether, residue was distilled to give 24.7 g of product,bp 103° C./1.3 kPa. ¹⁹F NMR: +45.4 (m, 1F), −82.4 (m, 2F), −83.5 (m,2F), −112.6 (t, J=2.6 Hz, 2F), −115.1 (t, J=15 Hz, 2F), −124.3 (s, 2F),−125.7 (t, J=14 Hz, 2F). HRMS: calcd for C₁₂H₁₁F₁₃SO₃: 482.0221. Found:482.0266.

Example 468 Hydrolysis of Copolymer

[1466] Copolymer containing 8.5 mol % of comonomer (1.5 g) was dissolvedin 30 mL of THF at room temperature. KOH (0.5 g) in 5 mL of ethanol and3 mL of water was added and the resulting mixture was stirred at roomtemperature for six hours. After removal of the solvent, residue wastreated with diluted HCl for 70 hours and then filtered to give solidswhich were washed with water, HCl and dried under full vacuum at 70° C.for two days to give 1.4 g solid.

Example 469 Hydrolysis of Copolymer

[1467] A mixture of 10.6 g of copolymer 5.0 g of KOH, 2 mL of water, 30mL of ethanol and 30 mL of THF was stirred at room temperature overnightand at 60 to 70° C. for 5 hours. After removal of a half of solvents,residue was treated with Conc. HCl to give rubbery material, which waspoured into a blender and blended with water for 30 min. Filtration gavesolids, which were washed with conc. HCl, and water and dried undervacuum at 60° C. overnight to give 8.7 g of dark rubbery material. ¹⁹FNMR(THF): −82.8 (br, 2F), −88.5 (br, 2F), −118.3 (br, 2F), −118.5 (br,2F).

Example 470 Hydrolysis of Homopolymer

[1468] A solution of 2.0 g of KOH in 25 mL of ethanol and 2 mL of wasterwas added to a flask with 3.0 g of homopolymer. The resultingheterogeneous mixture was stirred at room temperature overnight andheated to 60° C. for 2hours. After removal of one-half of liquid, thereaction mixture treated with 40 mL of conc. HCl for 30 min. Filtrationgave white solids which were washed with conc. HCl, and distilled waterand dried under vacuum at 60-70° C. for 24 hours to give 2.9 g of whitepowder.

Example 471

[1469] 1-Octadecene (8 mL, 8 vol %) was added to a suspension of[(2,6-iPrPh)₂DABAn]NiBr₂ (12 mg, 1.7×10⁻⁵ mol) in 100 mL of dry toluene.The flask was cooled to −1° C. using an Endocal® refrigeratedcirculating bath and 2.5 mL of a 7% MMAO solution in heptane was added.After stirring the reaction for 40 min, the flask was filled withpropylene (1 atm) and stirred for 20 minutes. The propylene was removedin vacuo and the reaction allowed to continue for an additional 40 min.Acetone and water were added to quench the polymerization andprecipitate the polymer. The resulting triblock polymer was dried underhigh vacuum overnight to yield 650 mg of a rubbery solid. GPC(trichlorobenzene, 135° C., polystyrene reference): M_(n)=60,100;M_(w)=65,500; M_(w)/M_(n)=1.09. DSC analysis: Two melt transitions wereobserved. T_(m)=8° C. (32 J/g), T_(m)=37° C. (6.5 J/g). ¹H-NMR analysis(CDCl₃): signals attributable to repeat units of propylene and1-octadecene were observed.

Example 472 Preparation of (2-i-Pr-6-MePh)₂DABAn

[1470] A Schlenk tube was charged with 2-isopropyl-6-methylaniline (5.00mL, 30.5 mmol) and acenaphthenequinone (2.64 g, 14.5 mmol). The reagentswere partially dissolved in 50 mL of methanol (acenaphthenequinone wasnot completely soluble) and 1-2 mL of formic acid was added. Anorange/yellow solid was collected via filtration after stirringovernight, and was washed with methanol and dried under vacuum.

Example 473 Preparation of (2-i-Pr-6-MePh)₂DABMe₂

[1471] A Schlenk tube was charged with 2-isopropyl-6-methylaniline (5.00mL, 30.5 mmol) and 2,3-butanedione (1.31 mL, 14.9 mmol). Methanol (5 mL)and one drop of concentrated HCl were added and the mixture was heatedto reflux with stirring for 30 minutes. The methanol and remaining dionewere removed under vacuum to give a dark, oily residue. The oil waschromatographed on a silica gel column using 10% ethyl acetate: 90%hexane as the eluent. The fractions containing the pure diimine werecombined and concentrated. The remaining solvents were removed undervacuum to give a pale yellow powder (0.9217 g, 17.75%).

Example 474 Preparation of [(2-i-Pr-6-MePh)₂DABAn]NiBr₂

[1472] Under inert conditions, a flame-dried Schlenk tube was chargedwith 0.50 g (1.13 mmol) of (2-i-Pr-6-MePh)₂DABAn, 0.34 g (1.10 mmol) of(DME)NiBr₂ and 25 mL of CH₂C₁₂. The reaction mixture was allowed to stirovernight. The solution was filtered and the solvent removed undervacuum. The residue was washed with ether (4×10 mL) to give anorange/yellow powder which was dried under vacuum overnight (0.68 g,94%).

Example 475 Preparation of [(2-i-Pr-6-MePh)₂DABMe₂]NiBr₂

[1473] Under inert conditions, a flame-dried Schlenk tube was chargedwith 0.3040 g (0.8722 mmol) of (2-i-Pr-6-MePh)₂DABMe₂, 0.2640 g (0.8533mmol) of (DME)NiBr₂ and 25 mL of CH₂Cl₂. The reaction mixture wasallowed to stir overnight. A solid was collected via filtration andwashed with ether (2×10 mL). Upon sitting, more solid precipitated fromthe supernatant. This precipitate was isolated via filtration, washedwith ether, and combined with the originally isolated product. Thecombined yellow/orange solids were dried under vacuum overnight (0.68 g,94%).

Example 476

[1474] Under a nitrogen atmosphere, the complex[(2-i-Pr-6-MePh)₂DABAn]NiBr₂ (0.0099 g, 1.5×10⁻⁵ mol) was placed into aflame-dried 250 mL Schlenk flask which was then evacuated andback-filled with propylene. Freshly distilled toluene (100 mL) was addedvia syringe and the resulting solution was stirred for five minutes atroom temperature. Polymerization was initiated with addition ofmethylaluminoxane (MAO; 1.5 mL 10% solution in toluene) and a propyleneatmosphere was maintained throughout the course of the reaction. Thereaction was stirred for two hours at constant temperature, at whichpoint the polymerization was by quenched with 6M HCl. Polymer wasprecipitated from the resulting solution with acetone, washed with waterand acetone, and dried under vacuum. Yield=3.09 g. DSC: T_(g) −31.2° C.GPC: M_(n)=142,000; M_(w)=260,000; M_(w)/Mn=1.83.

Example 477

[1475] Under a nitrogen atmosphere, the complex[(2-i-Pr-6-MePh)₂DABMe₂]NiBr₂ (0.0094 g, 1.5×10⁻⁵ mol) was placed into aflame-dried 250 mL Schlenk flask which was then evacuated andback-filled with propylene. Freshly distilled toluene (100 mL) was addedvia syringe and the resulting solution was stirred for five min at roomtemperature. Polymerization was initiated with addition ofmethylaluminoxane (MAO; 1.5 mL 10% solution in toluene) and a propyleneatmosphere was maintained throughout the course of the reaction. Thereaction was stirred for two hours at constant temperature, at whichpoint the polymerization was by quenched with 6M HCl. Polymer wasprecipitated from the resulting solution with acetone, washed with waterand acetone, and dried under vacuum. Yield=1.09 g. DSC: T_(g) −36.1° C.GPC: M_(n)=95,300; M_(w)=141,000; M_(w)/M_(n)=1.48.

Example 478

[1476] Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flaskwas charged with 40 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻⁵mol) of [(2-i-Pr-6-MePh)₂DABAn]NiBr₂, 10.0 mL of 1-hexene, and 50 mLmore toluene (100 mL total volume of liquid). The mixture was stirred ina room temperature water bath for 10 minutes and polymerization wasinitiated with addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for one hour at room temperature and wasquenched with 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=3.23 g. DSC: T_(g) −58.0° C.,T_(m) −16.5° C.

Example 479

[1477] Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flaskwas charged with 40 mL of freshly distilled toluene, 0.0125 g (2.0×10⁻⁵mol) of [(2-i-Pr-6-MePh)₂DABMe₂]NiBr₂, 10.0 mL of 1-hexene, and 50 mLmore toluene (100 mL total volume of liquid). The mixture was stirred ina room temperature water bath for 10 min and polymerization wasinitiated with addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for 22 h at room temperature and wasquenched with 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=2.10 g. DSC: T_(g) −56.4° C.,T_(m) 0.2° C.

Example 480

[1478] Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flaskwas charged with 40 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻⁵mol) of [(2-t-BuPh)₂DABAn]NiBr₂, 10.0 mL of 1-hexene, and 50 mL moretoluene (100 mL total volume of liquid). The mixture was stirred in anisopropanol bath maintained at approximately −10 to −12;C, andpolymerization was initiated with addition of 2.5 mL of MMAO (7.2%solution in heptane). The reaction mixture was stirred for two hours atconstant temperature and was quenched with acetone/water/6M HCl. Themixture was added to acetone to precipitate the polymer. After settlingovernight the polymer was collected via filtration, washed with waterand acetone, and dried under vacuum. Yield=0.35 g. DSC: (two broad melttransitions observed) T_(m)(1) 34.3° C., T_(m)(2) 66.4° C. Based on the¹H NMR spectrum, the polymer contains 41 methyl branches/1000 carbons(theoretical=55.5 Me/1000 C), indicating a high degree of chainstraightening.

Example 481

[1479] Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flaskwas charged with 25 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻⁵mol) of [(2-t-BuPh)₂DABAn]NiBr₂, 63 mL more toluene, and 12.0 mL of1-octadecene (100 mL total volume of liquid). The flask was cooled to−10° C. in a CO₂/isopropanol bath and stirred at this temperature forseveral minutes. The temperature was maintained at approximately −10° C.throughout the reaction by continually adding dry ice as needed.Polymerization of 1-octadecene was initiated with addition of 2.5 mL ofMMAO (7.2% solution in heptane). At 2 h, 10 min the reaction flask wastwice evacuated and back-filled with propylene. The polymerization wasstirred under one atmosphere of propylene for 20 min. The propylene wasremoved by repeatedly evacuating the flask and back-filling with argonuntil propylene evolution from the solution was no longer apparent. Thepolymerization was allowed to continue stirring in the presence of theremaining 1-octadecene until a total elapsed time of five hours wasreached. The reaction was quenched with acetone/water/6M HCl. Polymerwas precipitated in methanol/acetone, collected via filtration, washedwith water and acetone, and dried-under vacuum. Yield=1.03 g. DSC: T_(g)8.0° C., T_(m) 53.3° C. GPC: M_(n)=55,500; M_(w)=68,600;M_(w)/M_(n)=1.24. It is believed a block copolymer was formed.

Example 482 Preparation of [(2-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻

[1480] Under inert conditions, a flame-dried Schlenk tube was chargedwith 0.1978 g (3.404×10⁻⁴ mol) of [(2-t-BuPh)₂DABAn]PdMe₂ and 0.3451 g(3.408×10⁻⁴ mol) of H⁺(Et₂O)₂BAF⁻. The Schlenk tube was cooled to −78°C. and 10 mL of ether was added. The Schlenk tube was transferred to anice water bath and the reaction was stirred until the solids weredissolved and the color of the solution became deep red. The ether wasthen removed under vacuum to give a red, glassy solid that was crushedinto a powder (yield was quantitative).

Example 483 Preparation of [(2,5-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻

[1481] Following the procedure of Example 482, a red solid with thestructure [(2,5-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻ was obtained (quantitativeyield).

Example 484 Preparation of [(2-t-BuPh)₂DABMe₂]PdMe(NCMe)BAF⁻

[1482] Under inert conditions, a flame-dried Schlenk tube was chargedwith 0.1002 g (0.378 mmol) of (COD)PdMeCl and 0.3348 g (0.378 mmol) ofNaBAF. The Schlenk tube was cooled to −30° C. and 25 mL of CH₂Cl₂ and0.10 mL of NCMe were added via syringe. The reaction was stirred for twoh at −20 to −30° C. The resulting colorless solution was filtered intoanother cooled Schlenk tube, 20 mL of hexane was added, and the solventswere removed under vacuum to give a white powder [isolated(COD)PdMe(NCMe)BAF⁻]. This cationic precursor was combined with 0.138 g(0.396 mmol) of (2-t-BuPh)₂DABMe₂ in 50 mL of NCMe. The reaction mixturewas stirred overnight at room temperature. The solution was filtered andextracted with hexane (3×10 mL), and the solvents were removed undervacuum. The resulting yellow oil was dissolved in CH₂Cl₂/hexane and thesolvents were removed under vacuum to give a glassy solid that wascrushed into a powder. Two isomers were observed in solution by ¹H NMRspectroscopy. These two isomers arise from the coordination of theunsymmetrically substituted ligand in either the cis or trans fashion inregard to the t-butyl groups relative to the square plane of thecomplex.

Example 485 Polymerization of ethylene with[(2-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻

[1483] A flame-dried 250 mL Schlenk flask was charged with 0.1505 g(1.001×10⁻⁴ mol) of [(2-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻ in the glove box.The flask was twice evacuated and back-filled with ethylene and thencooled to −60° C. The solid was dissolved in 100 mL of CH₂Cl₂ and theflask was allowed to warm to room temperature with stirring under anatmosphere of ethylene. After stirring for 23 h the polymerization wasquenched with methanol. The solvent was removed under reduced pressureand the polymer was dissolved in petroleum ether and filtered throughsilica gel. The filtrate was concentrated and the remaining solvent wasremoved under vacuum to give a clear, colorless, viscous liquid.Yield=0.2824 g. ¹H NMR analysis: 125 Me/1000 CH₂.

Example 486

[1484] A flame-dried 250 mL Schlenk flask was charged with 0.1621 g(1.003×10⁻⁴ mol) of [(2,5-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻ in the glove box.The flask was twice evacuated and back-filled with ethylene and thencooled to −60° C. The solid was dissolved in 100 mL of CH₂Cl₂ and theflask was allowed to warm to room temperature with stirring under anatmosphere of ethylene. After stirring for 23 h the polymerization wasquenched with methanol. The solvent was removed under reduced pressureand the polymer was dissolved in petroleum ether and filtered throughsilica gel. The filtrate was concentrated and the remaining solvent wasremoved under vacuum to give a clear, colorless, viscous liquid.Yield=0.2809 g. ¹H NMR analysis: 136 Me/1000 C.H₂.

Example 487

[1485] A flame-dried 250 mL Schlenk flask was charged with 0.1384 g(1.007×10⁻⁴ mol) of [(2-t-BuPh)₂DABMe₂]PdMe(NCMe)BAF⁻ in the glove box.The flask was twice evacuated and back-filled with ethylene and thencooled to −60° C. The solid was dissolved in 100 mL of CH₂Cl₂ and theflask was allowed to warm to room temperature with stirring under anatmosphere of ethylene. After stirring for 23 h the polymerization wasquenched with methanol. The solvent was removed under reduced pressureand the polymer was dissolved in petroleum ether and filtered throughsilica gel. The filtrate was concentrated and the remaining solvent wasremoved under vacuum to give a clear, colorless, viscous liquid.Yield=2.40 g. ¹H NMR analysis: 123 Me/1000 CH₂.

Example 488

[1486] Under inert conditions, a Schlenk tube was charged with 0.0142 g(1.02×10⁻⁵ mol) of [(2-t-BuPh)₂DABAn]PdMe(Et₂O)BAF⁻. The Schlenk tubewas cooled to −78° C. and the solid was dissolved in 30 mL of CH₂Cl₂. A300 mL autoclave was charged with 70 mL of CH₂Cl₂ under an ethyleneatmosphere. The cold catalyst solution was quickly transferred viacannula into the Parr® reactor and the reactor was pressurized to 172kPa (absolute). The polymerization was stirred for 20 h and the ethylenepressure was released. The red/orange solution was transferred and thesolvent was removed under vacuum. A small amount of polyethyleneremained after drying under vacuum overnight. Yield=0.17 g. ¹H NMRanalysis: 120 Me/1000 CH₂.

Example 489

[1487] Following the procedure described in Example 488, 1.68 g ofpolyethylene was produced using 0.0140 g (1.02×10⁻⁵ mol) of[(2-t-BuPh)₂DABMe₂]PdMe(NCMe)BAF⁻. Yield=1.68 g. ¹H NMR analysis: 114Me/1000 CH₂.

Example 490

[1488] Under nitrogen, Ni(COD)₂ (0.017 g, 0.062 mmol) and(2,4,6-MePh)₂DABAn (0.026 g, 0.062 mmol) were dissolved in 2.00 g ofcyclopentene to give a purple solution. The solution was then exposed toair for several seconds. The resulting dark red-brown solution was thenput back under nitrogen, and EtAlCl₂ (1 M solution in toluene, 3.0 mL,3.0 mmol) was added. A cranberry-red solution formed instantly. Thereaction mixture was stirred at room temperature for 3 days, duringwhich time polycyclopentene precipitated. The reaction was then quenchedby the addition of methanol followed by several drops of concentratedHCl. The reaction mixture was filtered, and the product polymer washedwith methanol and dried to afford 0.92 g of polycyclopentene as anoff-white powder. Thermal gravimetric analysis of this sample showed aweight loss starting at 141° C.: the sample lost 18% of its weightbetween 141 and 470° C., and the remaining material decomposed between470 and 496° C.

Example 491

[1489] Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) andMeC(═N-2,6-C₆H₃-iPr₂)CH═C(NH—C₆H₃-iPr₂)Me (0.025 g, 0.06 mmol) weredissolved in benzene (5.0 mL). To the resulting solution was added HBAF(Et₂O)₂ (0.060 g, 0.06 mmol). The resulting solution was immediatelyfrozen inside a 40 mL shaker tube glass insert. The glass insert wastransferred to a shaker tube, and its contents allowed to thaw under anethylene atmosphere. The reaction mixture was agitated under 6.9 MPaC₂H₄ for 40 h at ambient temperature. The final reaction mixturecontained polyethylene, which was washed with methanol and dried; yieldof polymer=1.37 g. Branching per 1000 CH₂'s was determined by ¹³C NMR(C₆D₃Cl₃): Total methyls (10.2), Methyl (8.8), Ethyl (1.1), Propyl (0),Butyl (0), ≧Am and end of chains (3.2), ≧Bu and end of chains (0.3)

Example 492

[1490] Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) andthe ligand shown below (0.025 g, 0.06 mmol) were dissolved in benzene(5.0 mL). To the resulting solution was added HBAF (Et₂O)₂ (0.060 g,0.06 mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂H₄ for 18 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=11.0 g.

Example 493 {[(2,6-iPrPh)₂DABMe₂]Pd(η³-CHEtPh)]}BAF

[1491] In a nitrogen-filled drybox, 25 mL of Et₂O was added to a flaskcontaining [(2,6-iPrPh)₂DABMe₂]PdMeCl (402 mg, 0.716 mmol) and NaBAF(633 mg, 0.714 mmol) to yield an orange solution. Styrene (110 μL, 0.960mmol, 1.35 equiv) was dissolved in ˜10 mL of Et₂O and the resultingsolution was added to the reaction mixture, which was then stirred for 3h. Next, the solution was filtered and the solvent was removed in vacuo:The resulting orange powder (0.93 g, 87%) was washed with hexane anddried in vacuo. ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ7.76 (s, 8, BAF: H_(o)),7.59 (s, 4, BAF: H_(p)), 7.46-7.17 (m, 9, H_(aryl)), 6.29 (d, 1, J=7.33,H_(aryl)), 5.65 (d, 1, J=6.59, H_(aryl)), 3.33, 3.13, 2.37 and 1.93(septet, 1 each, J=6.97-6.72, CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 3.17 (dd,1, J=11.36, 3.66, CHEtPh), 2.22 and 2.17 (s, 3 each, N═C(Me)—C′(Me)═N),1.52, 1.45, 1.26, 1.26, 1.19, 1.15, 0.94 and 0.73 (d, 3 each,J=6.97-6.59, CHMeMe′, C′HMeMe′, C″HMeMe′, C′″HMeMe′), 0.88 (t, 3,J=0.88, CH(CH₂CH₃)Ph), 1.13 and −0.06 (m, 1 each, CH(CHH′CH₃)Ph); ¹³CNMR (CD₂Cl₂, 75 MHz, rt) δ176.6 and 174.0 (N═C—C′═N), 162.2 (q,J_(CB)=49.3, BAF: C_(ipso)) 142.8 and 142.4 (Ar, Ar′: C_(ipso)) 138.2,137.3, 137.1, and 136.9 (Ar, Ar′ : C_(o)), 135.2 (BAF: C_(o),C_(o)′),134.6 and 132.2 (Ph: C_(o), C_(m), or C_(p))), 129.4 (BAF: C_(m)), 129.0and 128.5 (Ar, Ar′: C_(p)), 125.1, 125.1, 124.9 and 124.7 (Ar, Ar′:C_(m)), 125.1 (q, J_(CF)=272.5, BAF: CF₃), 120.2 (Ph: C_(ipso)) and120.0 (Ph: C_(o), C_(m), or C_(p)), 117.9 (BAF: C_(p)), 103.0 and 88.6(Ph: C_(o)′and C_(m)′), 69.1(CHEtPh), 29.9, 29.7, 29.12 and 29.09(CHMe₂, C′HMe₂, C″HMe₂, C′″HMe₂), 24.4, 24.3, 23.5, 23.4, 23.1, 23.0,22.9, and 22.7 (CHMeMe′, C′HMeMe′, C″HMeMe′, C′″HMeMe′), 20.8, 20.65,and 20.61 (N═C(Me)—C′ (Me)═N, CH(CH₂CH₃)Ph)), 13.1 (CH(CH₂CH₃)Ph).

Example 494 {[(2,6-i-PrPh)₂DABH₂]Pd(η³-CHEt (4-C₆H₄-t-Bu) ]}BAF

[1492] t-Butylstyrene (230 μL, 1.26 mmol, 1.10 equiv) was added viamicroliter syringe to a mixture of [(2,6-i-PrPh)₂DABH₂]PdMeCl (611 mg,1.15 mmol) and NaBAF (1.01 g, 1.14 mmol) dissolved in 25 mL of Et₂O. Anadditional 25 mL of Et₂O was added to the reaction mixture, which wasthen stirred for ˜12 h. The resulting deep red solution was filtered,and the solvent was removed in vacuo to yield a sticky red solid. Thesolid was washed with 150 mL of hexane and the product was dried invacuo. A dull orange powder (1.59 g, 91.7%) was obtained: ¹H NMR(CD₂Cl₂, 400 MHz, rt) δ8.34 and 8.16 (s, 1 each, N═C(H)—C′(H)═N), 7.72(s, 8, BAF: H_(o)), 7.56 (s, 4, BAF: H_(p)), 7.5-7.1 (m, 8, H_(aryl)),6.88 (dd, 1, J=7.1, 1.9, H_(aryl)), 6.11 (dd, 1, J=7.3, 2.0, H_(aryl)),3.49, 3.37, 2.64 and 2.44 (septet, 1 each, J=6.6-6.9, CHMe₂, C′HMe₂,C″HMe₂ and C′″HMe₂), 3.24 (dd, 1, J=11.3, 4.1, CHEt(4-C₆H₄-t-Bu)), 1.52,1.48, 1.24, 1.24, 1.19, 1.18, 1.0 and 0.70 (d, 3 each, J=6.8-6.9,CHMeMe′, C′HMeMe′, C″HMeMe′, and C′″HMeMe′), 1.42 and 0.25 (m, 1 each,CH(CHH′CH₃) (4-C₆H₄-t-Bu)), 0.98 (s, 9, t-Bu), 0.87 (t, 3, J=7.4,CH(CH₂CH₃) (4-C₆H₄-t-Bu) ; ¹³C NMR (CD₂Cl₂, 100 MHz, rt) δ165.0(J_(CH)=165, N═C(H)), 163.3 (J_(CH)=165, N═C′(H)), 162.2 (q,J_(CB)=49.9, BAF: C_(ipso)) 157.0 (C₆H₄-t-Bu: C_(p)), 144.9 and 144.6(Ar, Ar′: C_(C) _(ipso)) 139.0, 138.4, 138.2 and 137.4 (Ar, Ar′: C_(o),C_(o)′) 135.2 (BAF: C_(o)), 133.3, 129.8, 129.6 and 129.2 (Ar, Ar′:C_(p); C₆H₄-t-Bu: C_(o), C_(m)), 129.3 (q, BAF: C_(m)), 125.0 (q,J_(CF)=272, BAF: CF₃), 124.7, 124.64, 124.55, and 124.3 (Ar, Ar′: C_(m),C_(m)′), 117.9 (BAF: C_(p)), 119.1, 116.4 and 94.9 (C₆H₄-t-Bu: C_(m)′,C_(ipso), C_(o)′), 68.5 (CHEt), 36.2 (CMe₃), 30.2 (CMe₃), 30.1, 29.9,28.80 and 28.77 (CHMe₂, C″HMe₂, C″HMe₂ and C′″HMe₂), 25.0, 24.8, 24.1,22.8, 22.7, 22.45, 22.36, and 22.1 (CHMeMe′, C′HMeMe′, C″HMeMe′ andC′″HMeMe′), 21.7 (CH(CH₂CH₃)), 13.2 (CH(CH₂CH₃)). Anal. Calcd for(C₇₁H₆₇BF₂₄N₂Pd): C, 56.05; H, 4.44; N, 1.84. Found: C, 56.24; H, 4.22;N, 1.59.

Example 495 {[(2,6-i-PrPh)₂DABMe₂]Pd(η³-CHEtC₆F₅)}BAF

[1493] A solution of H₂C═CHC₆F₅ (138 mg, 0.712 mmol) in 10 mL of Et₂Owas added to a mixture of [(2,6-i-PrPh)₂DABMe₂]PdMeCl (401 mg, 0.713mmol) and NaBAF (635 mg, 0.716 mmol) dissolved in 25 mL of Et₂O. Afterbeing stirred for 2 h, the reaction mixture was filtered and the solventwas removed in vacuo. An orange powder (937 mg, 83.0%) was obtained.

Example 496 {[(2,6-i-PrPh)₂DABH₂]Ni[η³-CHEt(4-C₆H₄-t-Bu)]}BAF

[1494] In the drybox, {[(2,6-i-PrPh)₂DABMe₂]NiMe(OEt₂)}BAF (22.4 mg,0.0161 mmol) was placed in an NMR tube. The tube was sealed with aseptum and Parafilm®, removed from the drybox, and cooled to −78° C.CD₂Cl₂ (700 μL) and H₂C═CH(4-C₆H₄-t-Bu) (15 μL, 5.10 equiv) were thenadded via gastight microliter syringe to the cold tube in sequentialadditions. The septum was sealed with a small amount of grease and moreParafilm, the tube was shaken briefly and then transferred to the cold(−78° C.) NMR probe. Insertion of t-butylstyrene was observed at −78° C.and was complete upon warming to −50° C. to yield the π-benzyl complex:¹H NMR (CD₂Cl₂, 400 MHz, −50;C) δ8.43 and 8.18 (s, 1 each,N═C(H)—C′(H)═N), 7.76 (s, 8, BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)),7.5-7.1 (m, 8, H_(aryl)), 6.80 (d, 1, J=7.3, H_(aryl)), 6.15 (d, 1,J=7.7, H_(aryl)), 3.72, 3.18, 2.68 and 2.50 (septet, 1 each, J=6.5-6.7,CHMe₂, C′HMe₂, C″HMe₂ and C′″HMe₂), 2.56 (dd, 1, J=11.5, 3.9, CHEt),1.6-0.8 (CHMeMe′, C′HMeMe′, C″HMeMe′, C′″HMeMe′, and CH(CHH′CH₃)), 0.94(s, 9, CMe₃), 0.72 (t, 3, J=7.3, CH(CH₂CH₃)), −0.04 (m, 1, CH(CHH′CH₃)).

Examples 497-515 General Procedure for the Synthesis of π-Allyl TypeNickel Compounds

[1495] A mixture of one equiv. of the appropriate α-diimine, one equivof NaBAF, and 0.5 equiv of [(allyl)Ni(μ-X)]₂ (X=Cl or Br) was dissolvedin Et₂O. The reaction mixture was stirred for ˜2 h before beingfiltered. The solvent was removed in vacuo to yield the desired product,generally as a red or purple powder. (The [(allyl)Ni(μ-X)]₂ precursorswere synthesized according to the procedures published in the followingreference: Wilke, G.; Bogdanovic, B.; Hardt, P.; Heimbach, P.; Keim, W.;Kroner, M.; Oberkirch, W.; Tanaka, K.; Steinrucke, E.; Walter, D.;Zimmermann, H. Angew. Chem. Int. Ed. Engl. 1966, 5, 151-164.) Thefollowing compounds were synthesized according to the above generalprocedure.

Example 497 {[(2,4,6-MePh)₂DABMe₂]Ni(η³-C₃H₅)}BAF Example 498{[(2,6-i-PrPh)₂DABMe₂]Ni(η³-C₃H₅)}BAF Example 499{[(2,6-i-PrPh)₂DABMe₂]Ni(η³-H₂CCHCHMe)}BAF Example 500{[(2,6-i-PrPh)₂DABMe₂]Ni(η³-H₂CCHCHPh)}BAF Example 501 {[(2,6-i-PrPh)₂DABMe₂]Ni(η³-H₂CCHCMe₂)}BAF Example 502{[(2,6-i-PrPh)₂DABAn]Ni(η³-C₃H₅)}BAF Example 503{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCHMe)}BAF Example 504{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCHPh)}BAF Example 505{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCMe₂)}BAF Example 506{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCHMe)}BAF Example 507{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCHPh)}BAF Example 508{[(2,4,6-MePh)₂DABAn]Ni(η³-C₃H₅)}BAF Example 509{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCMe₂)}BAF Example 510{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CC(COOMe)CH₂)}BAF Example 511{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CC(COOMe)CH₂)}BAF Example 512{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCH(COOEt)}BAF Example 513{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCH(COOEt)}BAF Example 514{[(2,6-i-PrPh)₂DABAn]Ni(η³-H₂CCHCHCl)}BAF Example 515{[(2,4,6-MePh)₂DABAn]Ni(η³-H₂CCHCHCl)}BAF Examples 516-537

[1496] Polymerizations catalyzed by nickel and palladium π-benzylinitiators and by nickel allyl initiators are illustrated in thefollowing Table containing Examples 516-537. The initiation ofpolymerizations catalyzed by nickel allyl initiators where the allylligand was substituted with functional groups, such as chloro or estergroups, was often aided by the addition of a Lewis acid. ExampleCompound Conditions Results 516 {[(2,6-i-PrPh)₂DABMe₂]Pd(η³- 0.067 mmolCmpd; 25° C.; 1 <0.5 g PE CHEtPh)}BAF atm E; 2 days; CH₂Cl₂ (270 TO) 517{[(2,6-i-PrPh)₂DABMe₂]Pd(η³- 0.027 mmol Cmpd; 25° C.; 8.2 g PECHEtPh)}BAF 6.9 MPa E; 18 h; C₆D₆ (11,000 TO) 518{[(2,6-i-PrPh)₂DABH₂]Pd(η³-CHEt(4- 0.016 mmol Cmpd; 25° C.; 1.5 g PEC₆H₄-t-Bu))}BAF 6.9 MPa E; 18 h; C₆D₆ (3,300 TO) 519{[(2,6-i-PrPh)₂DABMe₂]Pd(η³- 0.063 mmol Cmpd; 25° C.; 1 4.6 g PECHEtC₆F₅)}BAF atm E; 5 days; CH₂Cl₂ (2,600 TO) 520{[(2,6-i-PrPh)₂DABMe₂]Pd(η³- 0.044 mmol Cmpd; 25° C.; 6.4 g PECHEtC₆F₅)}BAF 6.9 MPa E; 18 h; C₆D₆ (5,200 TO) 521{[(2,4,6-MePh)₂DABAn]Ni(η³- 0.049 mmol Cmpd; 25° C.; 1.5 g PEH₂CCHCMe₂)}BAF 6.9 MPa E; 18 h; C₆D₆ (1,100 TO) 522{[(2,6-i-PrPh)₂DABMe₂]Ni(η³- 0.034 mmol Cmpd; 25° C.; 35 mg PEH₂CCHCMe₂)}BAF 6.9 MPa E; 18 h; C₆D₆ (37 TO) 523{[(2,4,6-MePh)₂DABMe₂]Ni(η³- 0.047 mmol Cmpd; 80° C.; 20 mg PE C₃H₅)}BAF6.9 MPa E; 18 h; C₆D₆ (15 TO) 524 {[(2,4,6-MePh)₂DABAn]Ni(η³- 0.034 mmolCmpd; 80° C.; 260 mg PE C₃H₅)}BAF 6.9 MPa E; 18 h; C₆D₆ (270 TO) 525{[(2,4,6-MePh)₂DABAn]Ni(η³- 0.026 mmol Cmpd; 80° C.; 141 mg PEH₂CCHCHPh)}BAF 6.9 MPa E; 18 h; C₆D₆ (190 TO) 526{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.040 mmol Cmpd; 80° C.; 992 mg PEH₂CCHCHPh)}BAF 6.9 MPa E; 18 h; C₆D₆ (880 TO) 527{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.043 mmol Cmpd; 80° C.; 23 mg PEH₂CCHCHMe)}BAF 6.9 MPa E; 18 h; C₆D₆ (19 TO) 528{[(2,6-i-PrPh)₂DABMe₂]Ni(η³- 0.044 mmol Cmpd; 80° C.; 54 mg PEH₂CCHCMe₂)}BAF 6.9 MPa E; 18 h; C₆D₆ (44 TO) 529{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.042 mmol Cmpd; 80° C.; 15 mg PE C₃H₅)}BAF6.9 MPa E; 18 h; C₆D₆ (13 TO) 530 {[(2,4,6-MePh)₂DABAn]Ni(η³- 0.043 mmolCmpd; 25° C.; 94 mg PE H₂CCHCHCl)}BAF 6.9 MPa E; 18 h; C₆D₆ (78 TO) 531{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.042 mmol Cmpd; 25° C.; 8 mg PEH₂CCHCHCl)}BAF 6.9 MPa E; 18 h; C₆D₆ (7 TO) 532{[(2,4,6-MePh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 0.04 7.8 g PEH₂CCHCHCl)}BAF mmol B(C₆F₅)₃; 25° C.; (14,000 6.9 MPa E; 18 h; CDCl₃ TO)533 {[(2,4,6-MePh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 0.04 8.4 g PEH₂CCHCHCl)}BAF mmol BPh₃; 25° C.; (15,000 6.9 MPa E; 18 h; CDCl₃ TO) 534{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 0.04 4.7 g PEH₂CCHCH(COOEt))}BAF mmol BPh₃; 25° C.; (8,400 TO) 6.9 MPa E; 18 h; CDCl₃535 {[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 0.04 6.8 g PEH₂CCHCHCl)}BAF mmol BPh₃; 80° C.; (12,000 6.9 MPa E; 18 h; C₆D₆ TO) 536{[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 10 mg 326 mg PEH₂CCHCHCl)}BAF montmorillonite; 80° C.; 6.9 (580 TO) MPa E; 18 h; C₆D₆537 {[(2,6-i-PrPh)₂DABAn]Ni(η³- 0.020 mmol Cmpd; 0.04 10.3 g PEH₂CCHCH(COOEt)}BAF mmol BPh₃; 80° C.; (18,000 6.9 MPa E; 18 h; C₆D₆

What is claimed is:
 1. A polyolefin, which contains about 80 to about150 branches per 1000 methylene groups, and which contains for every 100branches that are methyl, about 30 to about 90 ethyl branches, about 4to about 20 propyl branches, about 15 to about 50 butyl branches, about3 to about 15 amyl branches, and about 30 to about 140 hexyl or longerbranches.
 2. The polyolefin as recited in claim 1 which contains about100 to about 130 branches per 1000 methylene groups, and which containsfor every 100 branches that are methyl, about 50 to about 75 ethylbranches, about 5 to about 15 propyl branches, about 24 to about 40butyl branches, about 5 to about 10 amyl branches, and about 65 to about120 hexyl or longer branches.
 3. The polyolefin as recited in claim 1which is an ethylene homopolymer.
 4. A polyolefin which contains about20 to about 150 branches per 1000 methylene groups, and which containsfor every 100 branches that are methyl, about 4 to about 20 ethylbranches, about 1 to about 12 propyl branches, about 1 to about 12 butylbranches, about 1 to about 10 amyl branches, and 0 to about 20 hexyl orlonger branches.
 5. The polyolefin as recited in claim 4 which containsabout 40 to about 100 branches per 1000 methylene groups, and whichcontains for every 100 branches that are methyl, about 6 to about 15ethyl branches, about 2 to about 10 propyl branches, about 2 to about 10butyl branches, about 2 to about 8 amyl branches, and about 2 to about15 hexyl or longer branches.
 6. The polyolefin as recited in claim 4which is an ethylene homopolymer.
 7. A polymer, consisting essentiallyof units derived from the monomers ethylene and a compound of theformula CH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen, hydrocarbyl orsubstituted hydrocarbyl, and m is 0 or an integer from 1 to 16, andwhich contains about 0.01 to about 40 mole percent of repeat unitsderived from said compound, and provided that said repeat units derivedfrom said compound are in branches of the formula —CH(CH₂)_(n)CO₂R¹, inabout 30 to about 70 mole percent of said branches n is 5 or more, inabout 0 to about 20 mole percent n is 4, in about 3 to 60 mole percent nis 1, 2 and 3, and in about 1 to about 60 mole percent n is
 0. 8. Thepolymer as recited in claim 7 wherein m is
 0. 9. The polymer as recitedin claim 7 wherein R¹ is hydrocarbyl or substituted hydrocarbyl.
 10. Thepolymer as recited in claim 7 wherein R¹ is alkyl containing 1 to 10carbon atoms.
 11. The polymer as recited in claim 8 wherein R¹ ishydrocarbyl or substituted hydrocarbyl.
 12. The polymer as recited inclaim 7 wherein about 0.1 to about 20 mole percent of said units arederived from said compound.
 13. A process for the polymerization ofolefins, comprising, contacting a transition metal complex of abidentate ligand selected from the group consisting of

with an olefin wherein: said olefin is selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, norbornene, or a substitutednorbornene,; said transition metal is selected from the group consistingof Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd; R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸ taken togetherform a ring; R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; each R³⁰ is independently hydrogen, substitutedhydrocarbyl or hydrocarbyl, or two of R³⁰ taken together form a ring;R²⁰ and R²³ are independently hydrocarbyl or substituted hydrocarbyl;R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided that any olefinic bond in said olefinis separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms; R¹ ishydrogen, hydrocarbyl or substituted hydrocarbyl; n is 2 or 3; andprovided that: when said bidentate ligand is (XXX) M is not Pd; when Mis Pd a diene is not present; and said transition metal also has bondedto it a ligand that may be displaced by said olefin or add to saidolefin; when norbornene or substituted norbornene is used no otherolefin is present.
 14. The process as recited in claim 13 wherein saidtransition metal is Co, Fe, Ni or Pd.
 15. The process as recited inclaim 13 wherein said transition metal is Ni or Pd.
 16. The process asrecited in claim 13 or 15 wherein said olefin is ethylene, R¹⁷CH═CH₂, orcyclopentene, wherein R¹⁷ is n-alkyl.
 17. The process as recited inclaim 13 wherein said olefin comprises cyclopentene.
 18. The process asrecited in claim 13, 14, 15, or 16 wherein said bidentate ligand is(VIII).
 19. The process as recited in claim 18 wherein said olefin isethylene.
 20. The process as recited is in claim 18 wherein said olefinis propylene.
 21. The process as recited in claim 18 wherein said olefinis a combination of ethylene and propylene.
 22. The process as recitedin claim 18 wherein said olefin is contained in a mixed butenes stream.23. The process as recited in claim 18 wherein R² and R⁵ are eachindependently hydrocarbyl provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene to form a carbocyclic ring.
 24. The processas recited in claim 18 wherein R³ and R⁴ are each independently hydrogenor methyl or together are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 25. The process as recited in claim 18 whereinsaid olefin comprises cyclopentene.
 26. A process for thecopolymerization of an olefin and a fluorinated olefin, comprising,contacting a transition metal complex of a bidentate ligand selectedfrom the group consisting of

with an olefin, and a fluorinated olefin wherein: said olefin isselected from the group consisting of ethylene and an olefin of theformula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷; said transition metal is selected fromthe group consisting of Ni and Pd; said fluorinated olefin is of theformula H₂C═CH(CH₂)_(a)R_(f)R⁴²; a is an integer of 2 to 20; R_(f) isperfluoroalkylene optionally containing one or more ether groups; R⁴² isfluorine or a functional group; R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; each R¹⁷ isindependently saturated hydrocarbyl; and provided that said transitionmetal also has bonded to it a ligand that may be displaced by saidolefin or added to said olefin.
 27. The process as recited in claim 26wherein R⁴² is fluorine, ester or sulfonyl halide.
 28. The process asrecited in claim 26 wherein R_(f) is —(CF₂)_(b)—, wherein b is 2 to 20,or —(CF₂)_(d)OCF₂CF₂— wherein d is 2 to
 20. 29. The process as recitedin claim 26 or 27 wherein said olefin is ethylene or wherein said olefinis R¹⁷CH═CH₂, wherein R¹⁷ is n-alkyl.
 30. The process as recited inclaim 26 wherein R² and R⁵ are each independently hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring.
 31. A copolymer of an olefin of the formulaR¹⁷CH═CHR¹⁷ and a fluorinated olefin of the formulaH₂C═CH(CH₂)_(a)R_(f)R⁴², wherein: each R¹⁷ is independently hydrogen orsaturated hydrocarbyl; a is an integer of 2 to 20; R_(f) isperfluoroalkylene optionally containing one or more ether groups; andR⁴² is fluorine or a functional group; provided that when both of R¹⁷are hydrogen and R⁴² is fluorine, R_(f) is —(CF₂)_(b)— wherein b is 2 to20 or perfluoroalkylene containing at least one ether group.
 32. Thecopolymer as recited in claim 31 wherein R⁴² is fluorine, ester,sulfonic acid, or sulfonyl halide.
 33. The copolymer as recited in claim31 wherein R_(f) is —(CF₂)_(b)—, wherein b is 2 to 20, or—(CF₂)_(d)OCF₂CF₂— wherein d is 2 to
 20. 34. The copolymer as recited inclaim 31 or 32 wherein said olefin is ethylene or wherein said olefin isR¹⁷CH═CH₂, wherein R¹⁷ is n-alkyl.
 35. The copolymer as recited in claim31 wherein said fluorinated olefin is about 1 to 20 mole percent ofrepeat units in said copolymer.
 36. An acid catalyst of the compositionof claim 31, wherein R⁴² is sulfonic acid.
 37. A process for thepolymerization of olefins, comprising, contacting, at a temperature ofabout −100° C. to about +200° C.: a first compound W, which is a neutralLewis acid capable of abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻,provided that the anion formed is a weakly coordinating anion; or acationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion; a second compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, or norbornene; wherein: M is Ti,Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd in the m oxidationstate; y+z=m R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided that any olefinic bond in said olefinis separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms; Q isalkyl, hydride, chloride, iodide, or bromide; S is alkyl, hydride,chloride, iodide, or bromide; and provided that; when norbornene orsubstituted norbornene is present, no other monomer is present; when Mis Pd a diene is not present; and except when M is Pd, when both Q and Sare each independently chloride, bromide or iodide W is capable oftransferring a hydride or alkyl group to M.
 38. The process as recitedin claim 37 wherein said monomer is ethylene only.
 39. The process asrecited in claim 37 wherein said monomer is an α-olefin only.
 40. Theprocess as recited in claim 39 wherein said α-olefin is propylene. 41.The process as recited in claim 37 done in the presence of a solvent.42. The process as recited in claim 41 wherein R³ and R⁴ are eachindependently hydrogen or methyl, or R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl.
 43. Theprocess as recited in claim 37 used to make a block polymer.
 44. Theprocess as recited in claim 37 wherein: M is Ti(IV), Q and S arechloride, and y and z are 2; M is Zr(IV), Q and S are chloride, and yand z are 2; M is Co(II), Q and S are bromide, and y and z are 1; M isFe(II), Q and S are chloride, and y and z are 1; M is Sc(III), Q and Sare chloride, y is 1 and z is 2; M is Ni(II), Q and S are bromide orchloride, and y and z are 1; M is Pd(II), Q and S are methyl, and y andz are 1; M is Pd(II), Q and S are chloride, and y and z are 1; M isNi(I), Q is methyl, chloride, bromide, iodide or acetylacetonate, y is1, and z is 0; M is Pd(II), Q is methyl and S is chloride, and y and zare 1; or M is Ni(II), Q and S are methyl, and y and z are
 1. 45. Theprocess as recited in claim 37 wherein ethylene and propylene are themonomers.
 46. The process as recited in claim 37 wherein said monomersare part of a crude butenes stream.
 47. The process as recited in claim37 wherein R² and R⁵ are each independently hydrocarbyl, provided thatthe carbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring.
 48. The process as recited in claim 37 wherein saidmonomer comprises cyclopentene.
 49. A process for the production ofpolyolefins, comprising, contacting, at a temperature of about −100° C.to about +200° C., one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; and a compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; T¹ is hydrogen, hydrocarbyl not containingolefinic or acetylenic bonds, R¹⁵C(═O) or R¹⁵OC(═O)—; Z is a neutralLewis base wherein the donating atom is nitrogen, sulfur or oxygen,provided that if the donating atom is nitrogen then the pKa of theconjugate acid of that compound is less than about 6; X is a weaklycoordinating anion; R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds; each R¹⁷ is independently hydrocarbyl or substitutedhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms; M is Ni(II) or Pd(II); eachR¹⁶ is independently hydrogen or alkyl containing 1 to 10 carbon atoms;n is 1, 2, or 3; R⁸ is hydrocarbyl; and T² is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, hydrocarbyl substituted withketo or ester groups but not containing olefinic or acetylenic bonds,R¹⁵C(═O)— or R¹⁵OC(═O)—; provided that: when M is Pd, or (II) or (VII)are present, a diene is not present; and when norbornene or substitutednorbornene is used no other monomer is present.
 50. The process asrecited in claim 49 wherein said monomer is ethylene only.
 51. Theprocess as recited in claim 49 wherein said monomer is an α-olefin only.52. The process as recited in claim 51 wherein said α-olefin ispropylene.
 53. The process as recited in claim 49 wherein said compoundis (II), (IV) or (VII), M is Pd(II), and a comonomer selected from thegroup consisting of: a compound of the formula CH₂═CH(CH₂)_(m)CO₂R¹,wherein R¹ is hydrogen or, hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms, and m is 0 or an integer of 1 to 16;CO; and a vinyl ketone, is also present.
 54. The process as recited inclaim 53 wherein m is 0, and R¹ is hydrocarbyl or substitutedhydrocarbyl.
 55. The process as recited in claim 49 done in the presenceof a solvent.
 56. The process as recited in claim 49 done in the absenceof a solvent.
 57. The process as recited in claim 49 wherein R³ and R⁴are each independently hydrogen or methyl, or R³ and R⁴ taken togetherare 1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 58.The process as recited in claim 49 used to make a block polymer.
 59. Theprocess as recited in claim 49 wherein X is BAF, SbF₆, PF₆, or BF₄. 60.The process as recited in claim 57 wherein X is BAF, SbF₆, PF₆, or BF₄.61. The process as recited in claim 60 wherein a monomer is ethylene orpropylene.
 62. The process as recited in claim 49 wherein the monomersare ethylene and propylene.
 63. The process as recited in claim 49wherein said monomers are part of a crude butenes stream.
 64. Theprocess as recited in claim 49 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring.
 65. A process for theproduction of polyolefins, comprising contacting, at a temperature ofabout −100° C. to about +200° C., one or more monomers selected from thegroup consisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; with a compound of the formula

wherein: R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ ishydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R² takentogether form a ring; R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, andR²⁹ is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹taken together form a ring; each R³⁰ is independently hydrogen,substituted hydrocarbyl or hydrocarbyl or two of R³⁰ taken together forma ring; R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl; R²¹ and R²² are each in independently hydrogen, hydrocarbylor substituted hydrocarbyl; n is 2 or 3; T¹ is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; M isTi, Zr, Sc, Cr, a rare earth metal, V, Fe, Co, Ni or Pd the m oxidationstate; for (XVII), y+z=m; for (XIII), m is 2; Q is alkyl, hydride,chloride, iodide, or bromide; S is alkyl, hydride, chloride, iodide, orbromide; T² is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, hydrocarbyl substituted with keto or ester groups butnot containing olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; Zis a neutral Lewis base wherein the donating atom is nitrogen, sulfur oroxygen, provided that if the donating atom is nitrogen then the pKa ofthe conjugate acid of that compound is less than about 6; and X is aweakly coordinating anion; and provided that: when said compound is(XVII) M is not Pd; and except when M is Pd, when both Q and S are eachindependently chloride, bromide or iodide W is capable of transferring ahydride or alkyl group to M.
 66. The process as recited in claim 65wherein said monomer is ethylene only.
 67. The process as recited inclaim 65 wherein said monomer is an α-olefin only.
 68. The process asrecited in claim 67 wherein said α-olefin is propylene.
 69. The processas recited in claim 66 wherein M is Pd(II) and one or more comonomer isselected from the group consisting of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 70. Theprocess as recited in claim 69 wherein m is 0, and R¹ is hydrocarbyl orsubstituted hydrocarbyl.
 71. The process as recited in claim 65 done inthe presence of a solvent.
 72. The process as recited in claim 65 donein the absence of a solvent.
 73. The process as recited in claim 65 usedto make a block polymer.
 74. The process as recited in claim 65 whereinX is BAF, SbF₆, PF₆, or BF₄.
 75. The process as recited in claim 74wherein a monomer is ethylene or propylene.
 76. The process as recitedin claim 75 wherein the monomers are ethylene and propylene.
 77. Theprocess as recited in claim 65 wherein said monomers are part of a crudebutenes stream.
 78. The process as recited in claim 65 wherein: R⁴⁴ ishydrocarbyl, and R²⁸ is hydrogen or hydrocarbyl, or R⁴⁴ and R²⁸ takentogether form a ring; R⁴⁵ is hydrocarbyl, and R²⁹ is hydrogen orhydrocarbyl, or R⁴⁵ and R²⁹ taken together form a ring; each R³⁰ isindependently hydrogen or hydrocarbyl, or two of R³⁰ taken together forma ring; R²¹ and R²² are each in independently hydrogen or hydrocarbyl;and R²⁰ and R²³ are independently hydrocarbyl.
 79. A process for theproduction of polyolefins, comprising contacting, at a temperature ofabout −100° C. to about +200° C., one or more monomers selected from thegroup consisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; with a compound of the formula

wherein: R²⁰ and R²³ are independently hydrocarbyl or substitutedhydrocarbyl; R²¹ and R²² are each in independently hydrogen, hydrocarbylor substituted hydrocarbyl; X is a weakly coordinating anion; each R¹⁷is independently hydrocarbyl or substituted hydrocarbyl provided thatany olefinic bond in said olefin is separated from any other olefinicbond or aromatic ring by a quaternary carbon atom or at least twosaturated carbon atoms; M is Ni(II) or Pd(II); T² is hydrogen,hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbylsubstituted with keto or ester groups but not containing olefinic oracetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; and provided that: when M isPd a diene is not present; and when norbornene or substituted norborneneis used no other monomer is present.
 80. The process as recited in claim79 wherein said monomer is ethylene only.
 81. The process as recited inclaim 79 wherein said monomer is an α-olefin only.
 82. The process asrecited in claim 81 wherein said α-olefin is propylene.
 83. The processas recited in claim 79 wherein T² is methyl; R²⁰ and R²³ areindependently hydrocarbyl; and R²¹ and R²² are each in independentlyhydrogen or hydrocarbyl.
 84. A process for the production forpolyolefins, comprising contacting, at a temperature of about −100° C.to about +200° C., a first compound W, which is a neutral Lewis acidcapable of abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided thatthe anion formed is a weakly coordinating anion; or a cationic Lewis orBronsted acid whose counterion is a weakly coordinating anion; a secondcompound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, or norbornene; wherein: M is Ti,Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of oxidation state m;R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁴ and R²⁸ taken togetherform a ring; R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; each R³⁰ is independently hydrogen, substitutedhydrocarbyl or hydrocarbyl, or two of R³⁰ taken together form a ring; nis 2 or 3; y and z are positive integers; y+z=m; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; Q is alkyl, hydride, chloride, iodide, or bromide; S isalkyl, hydride, chloride, iodide, or bromide; and provided that; whennorbornene or substituted norbornene is present, no other monomer ispresent.
 85. The process as recited in claim 84 wherein R²⁸, R²⁹, andeach of R³⁰ are hydrogen.
 86. The process as recited in claim 84 whereinsaid monomer is ethylene only.
 87. The process as recited in claim 84wherein said monomer is an α-olefin only.
 88. The process as recited inclaim 87 wherein said α-olefin is propylene.
 89. The process as recitedin claim 84 done in the presence of a solvent.
 90. The process asrecited in claim 84 wherein both R⁴⁴ and R⁴⁵ are 2,4,6-trimethylphenyl.91. The process as recited in claim 84 used to make a block polymer. 92.The process as recited in claim 90 wherein a monomer is ethylene orpropylene.
 93. The process as recited in claim 84 wherein: M is Ti(IV),Q and S are chloride, and y and z are 2; M is Zr(IV), Q and S arechloride, and y and z are 2; M is Co(II), Q and S are bromide, and y andz are 1 ; M is Fe(II), Q and S are chloride, and y and z are 1; M isSc(III), Q and S are chloride, y is 1 and z is 2; M is Ni(II), Q and Sare bromide or chloride, and y and z are 1; M is Pd(II), Q and S arechloride, and y and z are 1; M is Pd(II), Q and S are methyl, and y andz are 1; M is Ni(I), Q is methyl, chloride, bromide, iodide oracetylacetonate, y is 1, and z is 0; M is Pd(II), Q is methyl and S ischloride, and y and z are 1; or M is Ni(II), Q and S are methyl, and yand z are
 1. 94. The process as recited in claim 84 wherein ethylene andpropylene are the monomers.
 95. The process as recited in claim 84wherein said monomers are part of a crude butenes stream.
 96. Theprocess as recited in claim 84 wherein: R⁴⁴ is hydrocarbyl, and R²⁸ ishydrogen or hydrocarbyl, or R⁴⁴ and R²⁸ taken together form a ring; R⁴⁵is hydrocarbyl, and R²⁹ is hydrogen or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; and each R³⁰ is independently hydrogen orhydrocarbyl, or two of R³⁰ taken together form a ring.
 97. A process forthe production of polyolefins, comprising, contacting, at a temperatureof about −100° C. to about +200° C., one or more monomers selected fromthe group consisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ orR¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; optionally a source of X⁻, and a compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a carbocyclic ring; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided thatR¹⁷ contains no olefinic bonds; T¹is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵C(═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds; E is halogen or —OR¹⁸; R¹⁸ is hydrocarbyl notcontaining olefinic or acetylenic bonds; and X is a weakly coordinatinganion; provided that when norbornene or substituted norbornene ispresent no other monomer is present.
 98. The process as recited in claim97 wherein said monomer is ethylene only.
 99. The process as recited inclaim 97 wherein said monomer is an α-olefin only.
 100. The process asrecited in claim 99 wherein said α-olefin is propylene.
 101. The processas recited in claim 97 wherein E is chlorine.
 102. The process asrecited in claim 97 wherein T¹ is alkyl.
 103. The process as recited inclaim 97 done in the presence of a solvent.
 104. The process as recitedin claim 98 wherein E is chlorine and T¹ is alkyl.
 105. The process asrecited in claim 104 wherein R³ and R⁴ are each independently hydrogenor methyl or R³ and R⁴ taken together are 1,8-naphthylylene, both R² andR⁵ are 2,6-diisopropylphenyl, and T¹ is methyl.
 106. The process asrecited in claim 97 used to make a block polymer.
 107. The process asrecited in claim 105 wherein X is BAF, SbF₆, PF₆, or BF₄.
 108. Theprocess as recited in claim 107 wherein a monomer is ethylene orpropylene.
 109. The process as recited in claim 97 wherein the monomersare ethylene and propylene.
 110. The process as recited in claim 97wherein said monomers are part of a crude butenes stream.
 111. Theprocess as recited in claim 97 wherein R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound directly to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a carbocyclic ring.
 112. A processfor the polymerization of olefins, comprising, contacting, at atemperature of about −100° C. to about +200° C.: a first compound W,which is a neutral Lewis acid capable of abstracting either Q⁻ or S⁻ toform WQ⁻ or WS³¹, provided that the anion formed is a weaklycoordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion; a second compound of theformula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, 4-vinylcyclohexene,cyclobutene, cyclopentene, substituted norbornene, and norbornene;wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; Q is alkyl, hydride, chloride, iodide,or bromide; S is alkyl, hydride, chloride, iodide, or bromide; andprovided that: when norbornene or substituted norbornene is present, noother monomer is present, and further provided that when4-vinylcyclohexene is present M is Ni; when M is Pd a diene is notpresent; and except when M is Pd, when both Q and S are eachindependently chloride, bromide or iodide W is capable of transferring ahydride or alkyl group to M.
 113. The process as recited in claim 112wherein said monomer is ethylene only.
 114. The process as recited inclaim 112 wherein said monomer is an α-olefin only.
 115. The process asrecited in claim 114 wherein said α-olefin is propylene.
 116. Theprocess as recited in claim 112 done in the presence of a solvent. 117.The process as recited in claim 112 wherein R³ and R⁴ are eachindependently hydrogen or methyl or both of R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 118.The process as recited in claim 112 used to make a block polymer. 119.The process as recited in claim 112 wherein a monomer is ethylene orpropylene.
 120. The process as recited in claim 112 wherein the molarratio of said first compound: said second compound (I) is about 5 toabout
 1000. 121. The process as recited in claim 112 wherein the molarratio of said first compound: said second compound (I) is about 10 toabout
 100. 122. The process as recited in claim 112 wherein said firstcompound is R⁹AlCl₂, R⁹ ₂AlCl, R⁹ ₃Al₂Cl₃, or an alkylaluminoxane inwhich the alkyl group has 1 to 4 carbon atoms, and wherein R⁹ is alkylcontaining 1 to 4 carbon atoms.
 123. The process as recited in claim 120wherein said first compound is R⁹AlCl₂, R⁹ ₂AlCl, R⁹ ₃Al₂Cl₃, or analkylaluminoxane in which the alkyl group has 1 to 4 carbon atoms, andwherein R⁹ is alkyl containing 1 to 4 carbon atoms.
 124. The process asrecited in claim 112 wherein the monomer comprises cyclopentene. 125.The process as recited in claim 112 wherein said monomers are part of acrude butenes stream.
 126. The process as recited in claim 112 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a carbocyclicring.
 127. A polymerization process, comprising, contacting a compoundof the formula [Pd(R¹³CN)₄]X₂, or a combination of Pd[OC(O)R⁴⁰]₂ and HX,with a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene, wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovidedR¹⁷ contains no olefinic bonds; R¹³ is hydrocarbyl; R⁴⁰ ishydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinatinganion; provided that when norbornene or substituted norbornene, ispresent no other monomer is present.
 128. The process as recited inclaim 127 wherein said monomer is ethylene only.
 129. The process asrecited in claim 127 wherein said monomer is an α-olefin only.
 130. Theprocess as recited in claim 129 wherein said α-olefin is propylene. 131.The process as recited in claim 127 wherein one or more comonomerselected from the group consisting of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 132. Theprocess as recited in claim 131 wherein m is 0, and R¹ is hydrocarbyl orsubstituted hydrocarbyl.
 133. The process as recited in claim 127 donein the presence of a solvent.
 134. The process as recited in claim 127wherein R³ and R⁴ are each independently hydrogen or methyl or both R³and R⁴ taken together are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 135. The process as recited in claim 127 used tomake a block polymer.
 136. The process as recited in claim 127 wherein Xis BAF, SbF₆, PF₆, or BF₄.
 137. The process as recited in claim 134wherein X is BAF or BF₄.
 138. The process as recited in claim 137wherein a monomer is ethylene or propylene.
 139. The process as recitedin claim 127 wherein the monomers are ethylene and propylene.
 140. Theprocess as recited in claim 127 wherein said monomers are part of acrude butenes stream.
 141. The process as recited in claim 127 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a carbocyclicring.
 142. A polymerization process, comprising, contacting: a Ni[0],Pd[0] or Ni[I] compound containing a ligand which may be displaced by aligand of the formula (VIII), (XXX), (XXXII) or (XXIII); a secondcompound of the formula

an oxidizing agent; a source of a relatively weakly coordinating anion;and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; each R³¹ is independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl; R⁴⁴ is hydrocarbyl or substituted hydrocarbyl,and R²⁸ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ andR²⁸ taken together form a ring; R⁴⁵ is hydrocarbyl or substitutedhydrocarbyl, and R²⁹ is hydrogen, substituted hydrocarbyl orhydrocarbyl, or R⁴⁵ and R²⁹ taken together form a ring; each R³⁰ isindependently hydrogen, substituted hydrocarbyl or hydrocarbyl, or twoof R³⁰ taken together form a ring; R⁴⁶ and R⁴⁷ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; n is 2 or 3; R⁴⁸ and R⁴⁹ are each independently hydrogen,hydrocarbyl, or substituted hydrocarbyl; R²⁰ and R²³ are independentlyhydrocarbyl or substituted hydrocarbyl; R²¹ and R²² are each inindependently hydrogen, hydrocarbyl or substituted hydrocarbyl; andprovided that; when norbornene or substituted norbornene is present, noother monomer is present; when a Pd[0] compound is used, a diene is notpresent; and when said second compound is (XXX) only an Ni[0] or Ni[I]compound is used.
 143. The process as recited in claim 142 wherein saidmonomer is ethylene only.
 144. The process as recited in claim 142wherein said monomer is an α-olefin only.
 145. The process as recited inclaim 144 wherein said α-olefin is propylene.
 146. The process asrecited in claim 142 done in the presence of a solvent.
 147. The processas recited in claim 142 used to make a block polymer.
 148. The processas recited in claim 142 wherein the monomers are ethylene and propylene.149. The process as recited in claim 142 wherein said monomers are partof a crude butenes stream.
 150. The process as recited in claim 142wherein: R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; each R¹⁷ is independently hydrocarbyl provided that any olefinicbond in said olefin is separated from any other olefinic bond oraromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; each R³¹ is independently hydrogen or hydrocarbyl; R⁴⁴ ishydrocarbyl, and R²⁸ is hydrogen or hydrocarbyl or R⁴⁴ and R²⁸ takentogether form a ring; R⁴⁵ is hydrocarbyl, and R²⁹ is hydrogen, orhydrocarbyl, or R⁴⁵ and R²⁹ taken together form a ring; each R³⁰ isindependently hydrogen or hydrocarbyl, or two of R³⁰ taken together forma ring; R⁴⁶ and R⁴⁷ are each independently hydrocarbyl, provided thatthe carbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R⁴⁸ and R⁴⁹ are each independently hydrogen orhydrocarbyl; R²⁰ and R²³ are independently hydrocarbyl; and R²¹ and R²²are each in independently hydrogen or hydrocarbyl.
 151. The process asrecited in claim 142 wherein said olefin comprises cyclopentene.
 152. Apolymerization process, comprising, contacting an Ni[0] complexcontaining a ligand or ligands which may be displaced by (VIII), oxygen,an alkyl aluminum compound, and a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; and eachR¹⁷ is independently hydrocarbyl or substituted hydrocarbyl providedthat any olefinic bond in said olefin is separated from any otherolefinic bond or aromatic ring by a quaternary carbon atom or at leasttwo saturated carbon atoms; provided that, when norbornene orsubstituted norbornene is present, no other monomer is present.
 153. Theprocess as recited in claim 152 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring.
 154. The process as recitedin claim 152 wherein said Ni[0] complex is a 1,5-cyclooctadiene complex.155. The process as recited in claim 152 wherein said monomer isethylene only.
 156. The process as recited in claim 152 wherein saidolefin comprises cyclopentene.
 157. The process as recited in claim 152wherein said monomer is an α-olefin only.
 158. The process as recited inclaim 157 wherein said α-olefin is propylene.
 159. The process asrecited in claim 152 done in the presence of a solvent.
 160. The processas recited in claim 156 used to make a block polymer.
 161. The processas recited in claim 152 wherein the monomers are ethylene and propylene.162. The process as recited in claim 152 wherein said monomers are partof a crude butenes stream.
 163. A polymerization process, comprising,contacting oxygen and an alkyl aluminum compound, or a compound of theformula HX, and a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; and eachR¹⁷ is independently hydrocarbyl or substituted hydrocarbyl providedthat any olefinic bond in said olefin is separated from any otherolefinic bond or aromatic ring by a quaternary carbon atom or at leasttwo saturated carbon atoms; X is a weakly coordinating anion; andprovided that, when norbornene or substituted norbornene is present, noother monomer is present.
 164. The process as recited in claim 163wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring.
 165. The process as recited in claim 142 wherein saidNi[0] compound is bis(1,5cycloocatdiene)nickel orbis(o-tolylphosphito)nickel(ethylene) or said Pd[0] compound istris(dibenzylideneacetone)dipalladium[0].
 166. The process as recited inclaim 163 wherein said monomer is ethylene only.
 167. The process asrecited in claim 163 wherein said olefin comprises cyclopentene. 168.The process as recited in claim 163 wherein said monomer is an α-olefinonly.
 169. The process as recited in claim 168 wherein said α-olefin ispropylene.
 170. The process as recited in claim 163 done in the presenceof a solvent.
 171. The process as recited in claim 163 used to make ablock polymer.
 172. The process as recited in claim 163 wherein themonomers are ethylene and propylene.
 173. The process as recited inclaim 163 wherein said monomers are part of a crude butenes stream. 174.The process as recited in claim 164 wherein said olefin comprisescyclopentene.
 175. The process as recited in claim 164 wherein saidmonomer is ethylene only.
 176. A polymerization process, comprising,contacting an Ni[0] complex containing a ligand or ligands which may bedisplaced by (VIII), HX or a Bronsted acidic solid, and a compound ofthe formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; and X is a weakly coordinating anion; provided that, whennorbornene or substituted norbornene is present, no other monomer ispresent.
 177. The process as recited in claim 176 wherein R² and R⁵ areeach independently hydrocarbyl, provided that the carbon atom bound tothe imino nitrogen atom has at least two carbon atoms bound to it; andR³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a carbocyclic ring.
 178. Theprocess as recited in claim 176 wherein said Ni[0] complex isbis(1,5-cycloocatidene)nickel or bis(o-tolylphosphito)nickel(ethylene)179. The process as recited in claim 176 wherein said monomer isethylene only.
 180. The process as recited in claim 176 wherein saidolefin comprises cyclopentene.
 181. The process as recited in claim 176wherein said monomer is an α-olefin only.
 182. The process as recited inclaim 181 wherein said α-olefin is propylene.
 183. The process asrecited in claim 176 done in the presence of a solvent.
 184. The processas recited in claim 176 used to make a block polymer.
 185. The processas recited in claim 176 wherein the monomers are ethylene and propylene.186. The process as recited in claim 176 wherein said monomers are partof a crude butenes stream.
 187. A process for the polymerization ofolefins, comprising, contacting, at a temperature of about −100° C. toabout +200° C.: a first compound W, which is a neutral Lewis acidcapable of abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided thatthe anion formed is a weakly coordinating anion; or a cationic Lewis orBronsted acid whose counterion is a weakly coordinating anion; a secondcompound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, or norbornene; wherein: M isNi(II) or Pd(II); R²⁰ and R²³ are independently hydrocarbyl orsubstituted hydrocarbyl; R²¹ and R²² are each in independently hydrogen,hydrocarbyl or substituted hydrocarbyl; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;Q is alkyl, hydride, chloride, iodide, or bromide; S is alkyl, hydride,chloride, iodide, or bromide; provided that; when norbornene orsubstituted norbornene is present, no other monomer is present; when Mis Pd a diene is not present; and except when M is Pd, when both Q and Sare each independently chloride, bromide or iodide W is capable oftransferring a hydride or alkyl group to M.
 188. The process as recitedin claim 187 wherein said monomer is ethylene only.
 189. The process asrecited in claim 187 wherein said monomer is an α-olefin only.
 190. Theprocess as recited in claim 189 wherein said α-olefin is propylene. 191.The process as recited in claim 187 done in the presence of a solvent.192. The process as recited in claim 187 used to make a block polymer.193. The process as recited in claim 191 wherein a monomer is ethyleneor propylene.
 194. The process as recited in claim 187 wherein the molarratio of said first compound: said second compound (I) is about 5 toabout 1000
 195. The process as recited in claim 187 wherein the molarratio of said first compound: said second compound (I) is about 10 toabout
 100. 196. The process as recited in claim 187 wherein the monomersare ethylene and propylene.
 197. The process as recited in claim 187wherein said monomers are part of a crude butenes stream.
 198. Theprocess as recited in claim 187 wherein R²⁰ and R²³ are independentlyhydrocarbyl; R²¹ and R²² are each in independently hydrogen orhydrocarbyl; and each R¹⁷ is independently hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms.
 199. A process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C., a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ does not contain any olefinic bonds; and each R²⁷ isindependently hydrocarbyl; each X is a weakly coordinating anion;provided that, when norbornene or substituted norbornene is present, noother monomer is present.
 200. The process as recited in claim 199wherein both R²⁷ are methyl.
 201. The process as recited in claim 199wherein said monomer is ethylene only.
 202. The process as recited inclaim 199 wherein said monomer is an α-olefin only.
 203. The process asrecited in claim 202 wherein said α-olefin is propylene.
 204. Theprocess as recited in claim 199 wherein one or more comonomer selectedfrom the group consisting of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 205. Theprocess as recited in claim 204 wherein m is 0, and R¹ is hydrocarbyl orsubstituted hydrocarbyl.
 206. The process as recited in claim 199 donein the presence of a solvent.
 207. The process as recited in claim 199wherein R³ and R⁴ are each independently hydrogen or methyl, and both R²and R⁵ are 2,6-diisopropylphenyl.
 208. The process as recited in claim199 used to make a block polymer.
 209. The process as recited in claim199 wherein X is BAF, SbF₆, PF₆, or BF₄.
 210. The process as recited inclaim 207 wherein X is BAF or BF₄.
 211. The process as recited in claim210 wherein a monomer is ethylene or propylene.
 212. The process asrecited in claim 199 wherein the monomers are ethylene and propylene.213. The process as recited in claim 199 wherein said monomers are partof a crude butenes stream.
 214. The process as recited in claim 199wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring, and each R¹⁷ is hydrocarbyl.
 215. The process asrecited in claim 199 wherein said olefin comprises cyclopentene.
 216. Aprocess for the polymerization of olefins, comprising, contacting, at atemperature of about −100° C. to about +200° C.: a first compound W,which is a neutral Lewis acid capable of abstracting either Q⁻ or S⁻ toform WQ⁻ or WS⁻, provided that the anion formed is a weakly coordinatinganion; or a cationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion; a second compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R⁴⁶ andR⁴⁷ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; R⁴⁸ and R⁴⁹ are each independentlyhydrogen, hydrocarbyl, or substituted hydrocarbyl; each R³¹ isindependently hydrocarbyl, substituted hydrocarbyl, or hydrogen; M isTi, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, Ni, or Pd of oxidationstate m; y and z are positive integers; y+z=m; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;Q is alkyl, hydride, chloride, iodide, or bromide; S is alkyl, hydride,chloride, iodide or bromide; and provided that; when norbornene orsubstituted norbornene is present, no other monomer is present; when Mis Pd a diene is not present; and except when M is Pd, when both Q and Sare each independently chloride, bromide or iodide W is capable oftransferring a hydride or alkyl group to M.
 217. The process as recitedin claim 216 wherein each R³¹ is hydrogen.
 218. The process as recitedin claim 216 wherein said monomer is ethylene only.
 219. The process asrecited in claim 216 wherein said monomer is an α-olefin only.
 220. Theprocess as recited in claim 219 wherein said α-olefin is propylene. 221.The process as recited in claim 216 done in the presence of a solvent.222. The process as recited in claim 216 wherein R⁴⁸ and R⁴⁹ are eachindependently hydrogen or methyl, both R⁴⁶ and R⁴⁷ are2,6-diisopropylphenyl, and T¹ is methyl.
 223. The process as recited inclaim 216 used to make a block polymer.
 224. The process as recited inclaim 216 wherein M is Ni(II).
 225. The process as recited in claim 216wherein M is Pd(II).
 226. The process as recited in claim 225 wherein amonomer is ethylene or propylene.
 227. The process as recited in claim216 wherein: M is Ti(IV), Q and S are chloride, and y and z are 2; M isZr(IV), Q and S are chloride, and y and z are 2; M is Co(II), Q and Sare bromide, and y and z are 1; M is Fe(II), Q and S are chloride, and yand z are 1; M is Sc(III), Q and S are chloride, y is 1 and z is 2; M isNi(II), Q and S are bromide or chloride, and y and z are 1; M is Pd(II),Q and S are methyl, and y and z are 1; M is Ni(I), Q is methyl,chloride, bromide, iodide or acetylacetonate, y is 1, and z is 0; or Mis Ni(II), Q and S are methyl, and y and z are
 1. 228. The process asrecited in claim 216 wherein the monomers are ethylene and propylene.229. The process as recited in claim 216 wherein said monomers are partof a crude butenes stream.
 230. The process as recited in claim 216wherein: R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R⁴⁸ and R⁴⁹ are eachindependently hydrogen, hydrocarbyl, or substituted hydrocarbyl; eachR³¹ is independently hydrocarbyl, substituted hydrocarbyl, or hydrogen;and each R¹⁷ is hydrocarbyl.
 231. The process as recited in claim 216wherein said olefin comprises cyclopentene.
 232. A compound of theformula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; T¹ is hydrogen, hydrocarbyl not containingolefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; Z is a neutralLewis base wherein the donating atom is nitrogen, sulfur or oxygen,provided that if the donating atom is nitrogen then the pKa of theconjugate acid of that compound is less than about 6; X is a weaklycoordinating anion; and R¹⁵ is hydrocarbyl not containing olefinic oracetylenic bonds; provided that when R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring Z is not an organic nitrile.233. The compound as recited in claim 232 wherein T¹ is methyl, and Z isR⁶ ₂O or R⁷CN wherein each R⁶ independently hydrogen or hydrocarbyl andR⁷ is hydrocarbyl.
 234. The compound as recited in claim 232 wherein R³and R⁴ are each independently hydrogen or methyl or R³ and R⁴ takentogether are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 235. The compound as recited in claim 233 whereinR³ and R⁴ are each independently hydrogen or methyl, and both R² and R⁵are 2,6-diisopropylphenyl, and wherein X is BAF, SbF₆, PF₆, or BF₄. 236.The compound as recited in claim 232 wherein X is BAF⁻, SbF₆ ⁻, PF₆ ⁻,or BF₄ ⁻.
 237. The compound as recited in claim 232 wherein R² and R⁵are each independently hydrocarbyl, provided that the carbon atom boundto the imino nitrogen atom has at least two carbon atoms bound to it;and R³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a carbocyclic ring.
 238. Thecompound as recited in claim 232 wherein each of R², R³, R⁴, R⁵, T¹, Z,and X are as follows: R² R³ R⁴ R⁵ T¹ Z X 2,6-i-PrPh Me Me 2,6-i-PrPh MeOEt₂ BAF 2,6-i-PrPh H H 2,6-i-PrPh Me OEt₂ BAF 2,6-MePh H H 2,6-MePh MeOEt₂ BAF 2,6-MePh Me Me 2,6-MePh Me OEt₂ BAF 2,6-i-PrPh Me Me 2,6-i-PrPhMe OEt₂ SbF₆ 2,6-i-PrPh Me Me 2,6-i-PrPh Me OEt₂ BF₄ 2,6-i-PrPh Me Me2,6-i-PrPh Me OEt₂ PF₆ 2,6-i-PrPh H H 2,6-i-PrPh Me OEt₂ SbF₆ 2,4,6-MePhMe Me 2,4,6-MePh Me OEt₂ SbF₆ 2,6-i-PrPh An An 2,6-i-PrPh Me OEt₂ SbF₆2,6-i-PrPh Me Me 2,6-i-PrPh Me NCMe SbF₆ Ph Me Me Ph Me NCMe SbF₆2,6-EtPh Me Me 2,6-EtPh Me NCMe BAF 2,6-EtPh Me Me 2,6-EtPh Me NCMe SbF₆2-t-BuPh Me Me 2-t-BuPh Me NCMe SbF₆ 1-Np Me Me 1-Np Me NCMe SbF₆ Ph₂CHH H Ph₂CH Me NCMe SbF₆ 2-PhPh Me Me 2-PhPh Me NCMe SbF₆ Ph a a Ph MeNCMe BAF Ph Me Me Ph Me NCMe SbF₆ Ph Ph Ph Ph Me NCMe BAF Ph₂CH H HPh₂CH Me NCMe SbF₆ Ph₂CH H H Ph₂CH Me SMe₂ SbF₆


239. A compound of the formula

wherein: R⁵⁰ is substituted phenyl; R⁵¹ is phenyl or substituted phenyl;R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; and provided that groups inthe 2 and 6 positions of R⁵⁰ have a difference in E_(s) of about 0.15 ormore.
 240. The compound as recited in claim 239 wherein groups in the 2and 6 of R⁵¹ have a difference in E_(s) of about 0.60 or more.
 241. Thecompound as recited in claim 239 wherein the group in the 2 position ofR⁵⁰ is t-butyl and the group in 6 position of R⁵⁰ is methyl or hydrogen.242. The compound as recited in claim 241 wherein the group in the 2position of R⁵¹ is t-butyl and the group in 6 position of R⁵¹ is methylor hydrogen.
 243. A compound of the formula

wherein: R⁵² is substituted phenyl; R⁵³ is phenyl or substituted phenyl;R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; Q is alkyl, hydride,chloride, bromide or iodide; S is alkyl, hydride, chloride, bromide oriodide; and provided that; groups in the 2 and 6 positions of R⁵² have adifference in E_(s) of 0.15 or more; and except when M is Pd, when bothQ and S are each independently chloride, bromide or iodide W is capableof transferring a hydride or alkyl group to M.
 244. The compound asrecited in claim 243 wherein said difference is about 0.20 more. 245.The compound as recited in claim 243 wherein groups in the 2 and 6 ofR⁵¹ have a difference in E_(s) of 0.15 or more.
 246. The compound asrecited in claim 243 wherein the group in the 2 position of R⁵² isi-propyl or t-butyl and the group in the 6 position of R⁵² is methyl orhydrogen.
 247. The compound as recited in claim 246 wherein the group inthe 2 position of R⁵³ is i-propyl or t-butyl and the group in 6 positionof R⁵² is methyl or hydrogen.
 248. A compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; T¹ is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl notcontaining an olefinic or acetylenic bond; Z is a neutral Lewis basewherein the donating atom is nitrogen, sulfur or oxygen, provided thatif the donating atom is nitrogen then the pKa of the conjugate acid ofthat compound is less than about 6; X⁻ is a weakly coordinating anion.249. The compound as recited in claim 248 wherein T¹ is methyl, Z is R⁶₂O wherein each R⁶ is independently alkyl, and X is BAF, SbF₆, PF₆, orBF₄.
 250. The compound as recited in claim 248 wherein R³ and R⁴ areeach independently hydrogen or methyl, and both R² and R⁵ are2,6-diisopropylphenyl.
 251. The compound as recited in claim 249 whereinR³ and R⁴ are each independently hydrogen or methyl, and both R² and R⁵are 2,6-diisopropylphenyl.
 252. The compound as recited in claim 248wherein R² and R⁵ are each independently hydrocarbyl provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring.
 253. A compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; M is Ni(II) or Pd(II); each R¹⁶ is independently hydrogenor alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3; X⁻ is aweakly coordinating anion; and R⁸ is hydrocarbyl.
 254. The compound asrecited in claim 253 wherein R³ and R⁴ are each independently hydrogenor methyl, both R² and R⁵ are 2,6-diisopropylphenyl, M is Pd(II), and Xis BAF, SbF₆, PF₆, or BF₄.
 255. The compound as recited in claim 254wherein each R¹⁶ is hydrogen and n is
 3. 256. The compound as recited inclaim 253 wherein M is Pd(II).
 257. The compound as recited in claim 253wherein each R¹⁶ is hydrogen and n is
 3. 258. The compound as recited inclaim 253 wherein R² and R⁵ are each independently hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring.
 259. A compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a ring; E is halogen or —OR¹⁸; R¹⁸ is hydrocarbyl not containingolefinic or acetylenic bonds; T¹ is hydrogen, hydrocarbyl not containingolefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC (═O)—; R¹⁵ ishydrocarbyl not containing olefinic or acetylenic bonds; and X⁻ is aweakly coordinating anion.
 260. The compound as recited in claim 259wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring.
 261. The compound as recited in claim 259 wherein T¹ is methyl,and E is chlorine.
 262. The compound as recited in claim 261 wherein R³and R⁴ are each independently hydrogen or methyl, and both R² and R⁵ are2,6-diisopropylphenyl.
 263. The compound as recited in claim 262 whereinX is BAF, SbF₆, PF₆, or BF₄.
 264. A compound of the formula[(η⁴-1,5-COD)PdT¹Z]⁺X⁻, wherein: T¹ is hydrocarbyl not containingolefinic or acetylenic bonds; X⁻ is a weakly coordinating anion; COD is1,5-cyclooctadiene; Z is R¹⁰CN; and R¹⁰ is hydrocarbyl not containingolefinic or acetylenic bonds.
 265. The compound as recited in claim 264wherein T¹ is methyl.
 266. The compound as recited in claim 265 whereinZ is methyl and X is BAF, SbF₆, PF₆, or BF₄.
 267. A compound of theformula

wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a ring; each R¹¹ is independently hydrogen, alkyl or—(CH₂)_(m)CO₂R¹; T³ is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, or —CH₂CH₂CH₂CO₂R⁸; P is a divalent group containingone or more repeat units derived from the polymerization of one or moreof ethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, or norbornene and,when M is Pd(II), optionally one or more of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinyl ketone; R⁸ is hydrocarbyl; m is 0or an integer from 1 to 16; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms; and X⁻ is aweakly coordinating anion.
 268. The compound as recited in claim 267wherein R¹ is hydrocarbyl or substituted hydrocarbyl.
 269. The compoundas recited in claim 267 wherein T³ is hydrogen or alkyl.
 270. Thecompound as recited in claim 267 wherein M is Pd(II).
 271. The compoundas recited in claim 269 wherein M is Pd(II).
 272. The compound asrecited in claim 267 wherein R³ and R⁴ are each independently hydrogenor methyl, and both R² and R⁵ are 2,6-diisopropylphenyl.
 273. Thecompound as recited in claim 271 wherein R³ and R⁴ are eachindependently hydrogen or methyl, and both R² and R⁵ are2,6-diisopropylphenyl.
 274. The compound as recited in claim 267 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a ring.
 275. Acompound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; T² is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, hydrocarbyl substituted with keto or ester groups butnot containing olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—;R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and X isa weakly coordinating anion.
 276. The compound as recited in claim 275wherein T² is methyl.
 277. The compound as recited in claim 276 whereinR³ and R⁴ are each independently hydrogen or methyl or R³ and R⁴ takentogether are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 278. The compound as recited in claim 276 whereinX is BAF, SbF₆, PF₆, or BF₄.
 279. The compound as recited in claim 275wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring.
 280. A process for the production of polyolefins, comprising,contacting, at a temperature of about −100° C. to about +200° C., acompound of the formula

with one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene,wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a ring; each R¹¹ is independently hydrogen, alkyl or—(CH₂)_(m)CO₂R¹; T³ is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, or —CH₂CH₂CH₂CO₂R⁸; P is a divalent group containingone or more repeat units derived from the polymerization of one ormonomers selected from the group consisting of ethylene, an olefin ofthe formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene,substituted norbornene, and norbornene, and, when M is Pd(II),optionally one or more of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinyl ketone; R⁸ is hydrocarbyl; each R¹⁷is independently hydrocarbyl or substituted hydrocarbyl provided thatany olefinic bond in said olefin is separated from any other olefinicbond or aromatic ring by a quaternary carbon atom or at least twosaturated carbon atoms; R¹ is hydrogen, or hydrocarbyl or substitutedhydrocarbyl containing 1 to 10 carbon atoms; m is 0 or an integer of 1to 16; and X is a weakly coordinating anion; provided that whennorbornene or substituted norbornene is present no other monomer ispresent; when M is Pd a diene is not present; and further provided thatwhen M is Ni(II) R¹¹ is not —CO₂R⁸.
 281. The compound as recited inclaim 280 wherein R² and R⁵ are each independently hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; and each R¹⁷ is hydrocarbyl.
 282. The process as recited in claim280 wherein T³ is methyl.
 283. The process as recited in claim 282wherein said monomer is ethylene only, and R¹¹ is hydrogen.
 284. Theprocess as recited in claim 282 wherein said monomer is an α-olefinonly, and R¹¹ is alkyl.
 285. The process as recited in claim 284 whereinsaid α-olefin is propylene, and R¹¹ is methyl.
 286. The process asrecited in claim 280 wherein M is Pd(II), and one or more comonomersselected from the group consisting of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 287. Theprocess as recited in claim 286 wherein m is 0, and R¹ is hydrocarbyl orsubstituted hydrocarbyl.
 288. The process as recited in claim 287wherein m is 0, and R¹ is hydrocarbyl or substituted hydrocarbyl. 289.The process as recited in claim 280 done in the presence of a solvent.290. The process as recited in claim 280 done in the absence of asolvent.
 291. The process as recited in claim 282 wherein R³ and R⁴ areeach independently hydrogen or methyl or R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 292.The process as recited in claim 280 used to make a block polymer. 293.The process as recited in claim 280 wherein X is BAF, SbF₆, PF₆, or BF₄.294. The process as recited in claim 291 wherein X is BAF, SbF₆, PF₆, orBF₄.
 295. The process as recited in claim 294 wherein a monomer isethylene or propylene.
 296. The process as recited in claim 280 whereinthe monomers are ethylene and propylene.
 297. The process as recited inclaim 280 wherein said monomers are part of a crude butenes stream. 298.The process as recited in claim 280 wherein said monomers comprisecyclopentene.
 299. A process for the production of polyolefins,comprising, contacting, at a temperature of about −100° C. to about+200° C., a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene, wherein: M is Zr,Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation statem; R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a ring; each R¹¹ is independently hydrogen or alkyl, or both ofR¹¹ taken together are hydrocarbylene to form a carbocyclic ring; T³ ishydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or—CH₂CH₂CH₂CO₂R⁸; Q is a monoanion; P is a divalent group containing oneor more repeat units derived from the polymerization of one or monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substitutednorbornene, and norbornene, and, when M is Pd(II), optionally one ormore of: a compound of the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinylketone; R⁸ is hydrocarbyl; a is 1 or 2; y+a+1=m; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms; m is 0 or an integer of 1 to 16; and Xis a weakly coordinating anion; provided that, when norbornene orsubstituted norbornene is present, no other monomer is present; when Mis Pd a diene is not present; and further provided that, when M isNi(II), T³ is not —CH₂CH₂CH₂CO₂R⁸.
 300. The process as recited in claim299 wherein R² and R⁵ are each independently hydrocarbyl, provided thatthe carbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; and each R¹⁷ is hydrocarbyl.
 301. The process as recited in claim299 wherein T³ is methyl.
 302. The process as recited in claim 301wherein said monomer is ethylene only, and R¹¹ is hydrogen.
 303. Theprocess as recited in claim 301 wherein said monomer is an α-olefinonly, and R¹¹ is alkyl.
 304. The process as recited in claim 303 whereinsaid α-olefin is propylene, and each R¹¹ is methyl or hydrogen.
 305. Theprocess as recited in claim 299 wherein M is Pd(II), and one or morecomonomer selected from the group consisting of: a compound of theformula CH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 306. Theprocess as recited in claim 305 wherein m is 0, and R¹ is hydrocarbyl orsubstituted hydrocarbyl.
 307. The process as recited in claim 299 donein the presence of a solvent.
 308. The process as recited in claim 299done in the absence of a solvent.
 309. The process as recited in claim301 wherein R³ and R⁴ are each independently hydrogen or methyl, andboth R² and R⁵ are 2,6-diisopropylphenyl.
 310. The process as recited inclaim 299 used to make a block polymer.
 311. The process as recited inclaim 299 wherein X is BAF, SbF₆, PF₆, or BF₄.
 312. The process asrecited in claim 309 wherein X is BAF, SbF₆, PF₆, or BF₄.
 313. Theprocess as recited in claim 312 wherein a monomer is ethylene orpropylene.
 314. The process as recited in claim 299 wherein the monomersare ethylene and propylene.
 315. The process as recited in claim 299wherein said monomers are part of a crude butenes stream.
 316. Theprocess as recited in claim 299 wherein said monomer comprisescyclopentene.
 317. A compound of the formula

wherein: M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd ofoxidation state m; R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; each R¹¹ is independentlyhydrogen, or alkyl, or both of R¹¹ taken together are hydrocarbylene toform a carbocyclic ring; T³ is hydrogen, hydrocarbyl not containingolefinic or acetylenic bonds, or —CH₂CH₂CH₂CO₂R⁸; P is a divalent groupcontaining one or more repeat units derived from the polymerization ofone or monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene, and optionally,when M is Pd(II), one or more of: a compound of the formula CH₂═CH(CH₂)_(m)CO₂R¹, CO, or a vinyl ketone; Q is a monovalent anion; R⁸ ishydrocarbyl; a is 1 or 2; y+a+1=m; each R¹⁷ is independently hydrocarbylor substituted hydrocarbyl provided that any olefinic bond in saidolefin is separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms; R¹ ishydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms; m is 0 or an integer of 1 to 16; and and X is a weaklycoordinating anion; and provided that when M is Pd a diene is notpresent;.
 318. The compound as recited in claim 317 wherein R¹ ishydrocarbyl or substituted hydrocarbyl.
 319. The compound as recited inclaim 317 wherein T³ is hydrogen or alkyl.
 320. The compound as recitedin claim 317 wherein R² and R⁵ are each independently hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; and R³ and R⁴ are each independentlyhydrogen, hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene toform a ring; and each R¹⁷ is hydrocarbyl.
 321. The compound as recitedin claim 317 wherein M is Pd(II).
 322. The compound as recited in claim319 wherein M is Pd(II).
 323. The compound as recited in claim 317wherein R³ and R⁴ are each independently hydrogen or methyl, and both R²and R⁵ are 2,6-diisopropylphenyl.
 324. The compound as recited in claim317 wherein both of R¹¹ taken together form a five-membered carbocyclicring.
 325. The compound as recited in claim 317 wherein both of R¹¹taken together are hydrocarbylene to form a carbocyclic ring.
 326. Aprocess, comprising, contacting, at a temperature of about −40° C. toabout +60° C., a compound of the formula [(η⁴-1,5-COD)PdT¹Z]⁺X⁻ and adiimine of the formula

to produce a compound of the formula

wherein: T¹ is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; X is a weakly coordinatinganion; COD is 1,5-cyclooctadiene; Z is R¹⁰CN; R¹⁰ is hydrocarbyl notcontaining olefinic or acetylenic bonds; R¹⁵ is hydrocarbyl notcontaining olefinic or acetylenic bonds; R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring.
 327. Theprocess as recited in claim 326 wherein R¹⁰ is alkyl, and T¹ is methyl.328. The process as recited in claim 326 carried out in a solvent of theformula R¹⁰CN, wherein R¹⁰ is hydrocarbyl not containing olefinic oracetylenic bonds.
 329. The process as recited in claim 327 wherein R³and R⁴ are each independently hydrogen or methyl, and both R² and R⁵ are2,6-diisopropylphenyl.
 330. The process as recited in claim 326 whereinX is BAF, SbF₆, PF₆, or BF₄.
 331. The process as recited in claim 326wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring.
 332. An ethylene homopolymer with a density of 0.86 g/ml or less.333. The ethylene homopolymer as recited in claim 332 wherein saiddensity is about 0.85 or less.
 334. A compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; each R²⁷ is hydrocarbyl; and each X is a weaklycoordinating anion.
 335. The compound as recited in claim 334 wherein R²and R⁵ are each independently hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; and R³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene to form a ring.
 336. Thecompound as recited in claim 334 wherein both of R²⁷ are methyl. 337.The compound as recited in claim 334 wherein R³ and R⁴ are eachindependently hydrogen or methyl or R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 338.The compound as recited in claim 334 wherein X is BAF, SbF₆, PF₆, orBF₄.
 339. A compound of the formula

wherein: M is Ni(II) or Pd(II); R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound directly to the imino nitrogen atom has at least two carbon atomsbound to it; R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; each R¹⁴ is independentlyhydrogen, alkyl or —(CH₂)_(m)CO₂R¹; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms; T⁴ is alkyl,—R⁶⁰C(O)OR⁸, R¹⁵(C═O)— or R¹⁵OC(═O)—; R¹⁵ is hydrocarbyl not containingolefinic or acetylenic bonds; R⁶⁰ is alkylene not containing olefinic oracetylenic bonds; R⁸ is hydrocarbyl;; and X is a weakly coordinatinganion; and provided that when R¹⁴ is —(CH₂)_(m)CO₂R¹, or T⁴ is notalkyl, M is Pd(II).
 340. The compound as recited in claim 339 wherein R²and R⁵ are each independently hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; and R³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³and R⁴ taken together are hydrocarbylene to form a ring.
 341. Thecompound as recited in claim 339 wherein T⁴ is methyl and M is Pd(II).342. The compound as recited in claim 339 wherein each R¹⁴ isindependently hydrogen or —(CH₂)_(m)CO₂R¹ and M is Pd(II).
 343. Ahomopolypropylene with a glass transition temperature of −30° C. orless, provided that said homopolypropylene has at least 50 branches per1000 methylene groups.
 344. The homopolypropylene as recited in claim343 wherein said glass transition temperature is about −35° C. or less.345. A homopolymer of cyclopentene having a degree of polymerization ofabout 30 or more and an end of melting point of about 100° C. to about320° C., provided that said homopolymer has less than 5 mole percent ofenchained linear olefin containing pentylene units.
 346. The homopolymeras recited in claim 345 wherein at least 90 percent of repeat units are1,3-cyclopentylene repeat units.
 347. The homopolymer as recited inclaim 345 wherein at least 90 percent of repeat units arecis-1,3-cyclopentylene repeat units.
 348. The homopolymer as recited inclaim 345 wherein an X-ray powder diffraction pattern thereof hasreflections at approximately 17.3°, 19.3°, 24.2°, and 40.7°2θ.
 349. Ahomopolymer of cyclopentene that has an X-ray diffraction pattern withreflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ.
 350. Thehomopolymer as recited in claim 349 which has a monoclinic unit cell ofthe approximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; andg=123.2°.
 351. The homopolymer as recited in claim 349 wherein at least90 percent of repeat units are 1,3-cyclopentylene repeat units.
 352. Thehomopolymer as recited in claim 351 wherein at least 90 percent ofrepeat units are cis-1,3-cyclopentylene repeat units.
 353. A homopolymerof cyclopentene wherein at least 90 mole percent of enchainedcyclopentylene units are 1,3-cyclopentylene units, and said homopolymerhas an average degree of polymerization of 30 more.
 354. A homopolymerof cyclopentene wherein at least 90 mole percent of enchainedcyclopentylene units are cis-1,3-cyclopentylene, and said homopolymerhas an average degree of polymerization of about 10 or more.
 355. Acopolymer of cyclopentene and ethylene wherein at least 75 mole percentof enchained cyclopentylene units are 1,3-cyclopentylene units.
 356. Thecopolymer as recited in claim 355 wherein at least 50 mole percent ofthe repeat units are derived from cyclopentene.
 357. The copolymer asrecited in claim 355 wherein there are at least 20 branches per 1000methylene carbon atoms.
 358. A copolymer of cyclopentene and ethylenewherein there are at least 20 branches per 1000 methylene carbon atoms.359. The copolymer as recited in claim 358 wherein at least 50 molepercent of the repeat units are derived from ethylene.
 360. A copolymerof cyclopentene and ethylene wherein at least 50 mole percent of therepeat units are derived from cyclopentene.
 361. A copolymer comprisingrepeat units of cyclopentene and an α-olefin.
 362. The copolymer asrecited in claim 361 wherein repeat units derived from ethylene are alsopresent.
 363. The copolymer as recited in claim 361 wherein saidα-olefin is a linear α-olefin.
 364. The copolymer as recited in claim361 wherein at least 90 mole percent of repeat units derived fromcyclopentene are 1,3-cyclopentylene units.
 365. The copolymer as recitedin claim 364 wherein at least 90 mole percent of repeat units derivedfrom cyclopentene are cis-1,3-cyclopentylene units.
 366. A fiber madefrom the polymer of claim 345, 349, 353, 354, 355, 356, 357, 358, 360 or361.
 367. A polymerization process, comprising, contacting an olefin ofthe formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, each R¹⁷ is independentlyhydrogen, hydrocarbyl, or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms with a catalyst, wherein said catalyst: contains a nickelor palladium atom in a positive oxidation state; contains a neutralbidentate ligand coordinated to said nickel or palladium atom, andwherein coordination to said nickel or palladium atom is through twonitrogen atoms or a nitrogen atom and a phosphorous atom; and saidneutral bidentate ligand, has an Ethylene Exchange Rate of less than20,000 L-mol⁻¹s⁻¹ when said catalyst contains a palladium atom, and lessthan 50,000 L-mol⁻¹s⁻¹ when said catalyst contains a nickel atom; andprovided that when M is Pd a diene is not present.
 368. Thepolymerization process as recited in claim 367 wherein said EthyleneExchange Rate is less than 10,000 L-mol⁻¹s⁻¹ when said catalyst containsa palladium atom, and less than 25,000 L-mol⁻¹s⁻¹ when said catalystcontains a nickel atom.
 369. The process as recited in claim 367 whereinsaid bidentate ligand is coordinated to said nickel or palladium atomthrough two nitrogen atoms.
 370. The process as recited in claim 369wherein said ligand is an α-diimine.
 371. The process as recited inclaim 367 wherein said olefin has the formula R¹⁷CH═CH₂, wherein R¹⁷ ishydrogen or n-alkyl.
 372. A process for the polymerization of olefins,comprising, contacting, at a temperature of about −100° C. to about+200° C.: a first compound which is a source of a relativelynoncoordinating monoanion; a second compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, or norbornene; wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that R¹⁷does not contain any olefinic bonds; T¹ is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, R¹⁵C(═O)— or R¹⁵OC(═O)—; S ischloride, iodide, or bromide; and provided that, when norbornene orsubstituted norbornene is present, no_other monomer is present.
 373. Theprocess as recited in claim 372 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring; and each R¹⁷ is saturated hydrocarbyl.374. The process as recited in claim 372 wherein said source is analkali metal salt of said anion.
 375. The process as recited in claim372 wherein T¹ is methyl.
 376. The process as recited in claim 372wherein said monomer is ethylene only, and R¹¹ is hydrogen.
 377. Theprocess as recited in claim 372 wherein one or more comonomer selectedfrom the group consisting of: a compound of the formulaCH₂═CH(CH₂)_(m)CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0 oran integer of 1 to 16; CO; and a vinyl ketone is also present.
 378. Theprocess as recited in claim 372 done in the presence of a solvent. 379.The process as recited in claim 368 used to make a block polymer. 380.The process as recited in claim 368 wherein said monoanion is BAF, SbF₆,PF₆, or BF₄.
 381. The process as recited in claim 374 wherein saidmonoanion is BAF⁻, SbF₆ ⁻, PF₆ ³¹, or BF₄ ⁻.
 382. The process as recitedin claim 377 wherein a monomer is ethylene or propylene.
 383. Theprocess as recited in claim 372 wherein the monomers are ethylene andpropylene.
 384. A polyolefin, comprising, a polymer made by polymerizingone or more monomers of the formula H₂C═CH(CH₂)_(e)G by contacting saidmonomers with a transition metal containing coordination polymerizationcatalyst, wherein: each G is independently hydrogen or —CO₂R¹; each e isindependently 0 or an integer of 1 to 20; each R¹ is independentlyhydrogen, hydrocarbyl or substituted hydrocarbyl; and provided that:said polymer has at least 50 branches per 1000 methylene groups; in atleast 50 mole percent of said monomers G is hydrogen; except when nobranches should be theoretically present, the number of branches per1000 methylene groups is 90% or less than the number of theoreticalbranches per 1000 methylene groups, or the number of branches per 1000methylene groups is 110% or more of theoretical branches per 1000methylene groups; and when there should be no branches theoreticallypresent, said polyolefin has 50 or more branches per 1000 methylenegroups; and provided that said polyolefin has at least two branches ofdifferent lengths containing less than 6 carbon atoms each.
 385. Thepolyolefin as recited in claim 384 wherein except when no branchesshould be theoretically present the number of branches per 1000methylene groups is 80% or less than the number of theoretical branchesper 1000 methylene groups, or the number of branches per 1000 methylenegroups is 120% or more of theoretical branches per 1000 methylenegroups; and when there should be no branches theoretically present, saidpolyolefin has 75 or more branches per 1000 methylene groups.
 386. Apolyolefin, comprising, a polymer made by polymerizing one or moremonomers of the formula H₂C═CH(CH₂)_(e)G by contacting said monomerswith a transition metal containing coordination polymerization catalyst,wherein: each G is independently hydrogen or —CO₂R¹; each e isindependently 0 or an integer of 1 to 20; R¹ is independently hydrogen,hydrocarbyl or substituted hydrocarbyl; and provided that: said polymerhas at least 50 branches per 1000 methylene groups; in at least 50 molepercent of said monomers G is hydrogen; said polymer has at least 50branches of the formula —(CH₂)_(f)G per 1000 methylene groups, whereinwhen G is the same as in a monomer and e≠f, and/or for any singlemonomer of the formula H₂C═CH(CH₂)_(e)G there are less than 90% of thenumber of theoretical branches per 1000 methylene groups, or more than110% of the theoretical branches per 1000 methylene groups of theformula —(CH₂)_(f)G and f=e, and wherein f is 0 or an integer of 1 ormore; and provided that said polyolefin has at least two branches ofdifferent lengths containing less than 6 carbon atoms each.
 387. Thepolyolefin as recited in claim 386 wherein when G is the same as in amonomer and e≠f, and/or for any single monomer of the formulaH₂C═CH(CH₂)_(e)G there are less than 80% of the number of theoreticalbranches per 1000 methylene groups, or more than 120% of the theoreticalbranches per 1000 methylene groups of the formula —(CH₂)_(f)G and f=e.388. A tackifier for an adhesive comprising the polymer of claim 1, 2,3, 5, 6 or
 7. 389. An oil additive for smoke suppression in two-strokegasoline engines comprising the polymer of claim 1, 2, 3, 4, 5, 6, or 7.390. A base resin for a hot melt adhesive, a pressure sensitive adhesiveor a solvent applied adhesive comprising the polymer of claim 1, 2, 3,4, 5, 6 or
 7. 391. A viscosity modifier for lubricating oils comprisingthe polymer of claim 1, 2, 3, 4, 5, 6 or
 7. 392. A coating or penetrantcomprising the polymer of claim 1, 2, 4, 5, 6 or
 7. 393. A base polymerfor caulking comprising the polymer of claim 1, 2, 3, 4, 5, 6 or
 7. 394.The polymer of claim 1, 2, 4, 5, 6 or 7 which is grafted so it containsfunctional groups.
 395. A toughener for a thermoplastic or a thermosetcomprising the polymer of claim
 14. 396. A modifier for asphaltcomprising the polymer of claim 1, 3, 4, 6, 7, 332 or
 343. 397. Thepolymer of claim 1, 3, 4, 6, 7, 332 or 343 which is chlorinated orchlorosulfonated.
 398. The polymer of claim 17 which is elastomeric.399. A wire insulation or jacketing comprising the polymer of claim 1,3, 4, 6, 7, 332 or
 343. 400. A toughener for polyolefins comprising thepolymer of claim 1, 3, 4, 6, 7, 332 or
 343. 401. A base for a syntheticlubricant comprising the polymer of claim 1, 4, 6, 7, 332 or
 343. 402. Adrip suppressant for synthetic polymers comprising the polymer of claim1, 3, 4, 6, 7, 332 or
 343. 403. A blown or cast film, or a sheetcomprising the polymer of claim 1, 3, 4, 6, 7, 332 or
 343. 404. Anadditive for wax candles for smoke suppression or drip controlcomprising the polymer of claim 1, 4, 6, 7, 332 or
 343. 405. A baseresin for carpet backing comprising the polymer of claim 1, 3, 4, 6, 7,332 or
 343. 406. A capliner resin comprising the polymer of claim 1, 3,4, 6, 7, 332 or
 343. 407. A thermal transfer imaging resin comprisingthe polymer of claim 1, 4, 6, 7, 332 or
 343. 408. An extrusion orcoextrusion onto a plastic, metal, textile or paper web comprising thepolymer of claim 1, 3, 4, 6, 7, 332 or
 343. 409. A laminating adhesivefor glass comprising the polymer of claim 1, 3, 4, 6, 7, 332 or 343.410. A foamed object comprising the polymer of claim 1, 3, 4, 6, 7, 332or
 343. 411. A powder used to coat an object comprising the polymer ofclaim 1, 3, 4, 6, 7, 332 or
 343. 412. A hose comprising the polymer ofclaim 1, 3, 4, 6, 7, 332 or
 343. 413. A pour point depressant for a fuelor oil comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
 343. 414. Anonwoven fabric comprising the polymer of claim 1, 3, 4, 6, 7, 332 or343.
 415. A roofing membrane comprising the polymer of claim 1, 3, 4, 6,7, 332 or
 343. 416. A reactive diluent for an automotive finishcomprising the polymer of claim 7, 8, 9, 10, 11 or
 12. 417. An ionomercomprising the polymer of claim 7, 8, 9, 10, 11 or
 12. 418. A moldingresin comprising the ionomer of claim
 417. 419. A core for theinitiation of condensation polymerizations yielding a grafted branchedpolymer, comprising the polymer of claim 7, 8, 9, 10, 11, or
 12. 420. Acompatiblizing agent comprising the polymer of claim 3, 6 or
 7. 421. Atoughener for a thermoplastic or thermoset comprising the polymer ofclaim 1, 3, 4, 6, 7, 332 or
 343. 422. An internal plasticizer forpolymers comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
 343. 423.An adhesive for adhering a polymer comprising the polymer of claim 3, 6,7, 332 or
 343. 424. A curing agent for a polymer containingcomplimentary functional groups comprising the polymer of claim 3, 6 or7.
 425. An additive to thermoplastic polymers to improve the adhesion ofpaint thereto comprising the polymer of claim 3, 6 or
 7. 426. A polymerblend comprising the polymer of claim 1, 3, 4, 6, 7, 332 or 343 and atleast one other polymer.
 427. A polymer of one or more alpha-olefins ofthe formula CH₂═CH(CH₂)_(a)H wherein a is an integer of 2 or more, whichcontains the structure

wherein R³⁵ is an alkyl group and R³⁶ is an alkyl group containing twoor more carbon atoms, and provided that R³⁵ is methyl in at least about2 mole percent of the total amount of (XXV) in said polymer.
 428. Thepolymer as recited in claim 427 wherein a structure in which R³⁵ ismethyl is about 5 mole percent or more of the total amount of (XXV) insaid polymer.
 429. The polymer as recited in claim 427 wherein astructure in which R³⁵ is methyl is about 50 mole percent or more of thetotal amount of (XXV) in said polymer.
 430. A polymer of one or morealpha-olefins of the formula CH₂═CH(CH₂)_(a)H wherein a is an integer of2 or more, wherein said polymer contains methyl branches and said methylbranches are about 25 to about 75 mole percent of the total branches insaid polymer.
 431. The polymer as recited in claim 430 which containsbranches of the formula —(CH₂)_(a)H.
 432. The polymer as recited inclaim 430 which contains branches of the formula —(CH₂)_(n)H wherein nis an integer of 6 or greater.
 433. The polymer as recited in claim 431which contains the structure

and wherein (XXVI) is present in an amount of 0.5 branches of (XXVI) ormore per 1000 methylene atoms greater than can be accounted for by endgroups.
 434. A polyethylene containing the structure (XXVII) in anamount greater than can be accounted for by end groups.


435. The polyethylene as recited in claim 434 which contains about 2 ormore of (XXVII) per 1000 methylene groups in said polymer.
 436. Apolypropylene containing one or both of the structures (XXVIII) and(XXIX), provided that: (XXIX), if present is present in an amountgreater than or equal to 0.5 of (XXIX) per 1000 methylene groups greaterthan can be accounted for by end groups; or the polymer contains atleast 0.5 or more of (XXVIII) per 1000 methylene groups, if (XXVIII) ispresent.


437. The polypropylene as recited in claim 436 which contains about 15or more groups of structure (XXVIII) per 1000 methylene groups in saidpolypropylene.
 438. The polypropylene as recited in claim 436 whichcontains about 15 or more groups of structure (XXIX) per 1000 methylenegroups in said polypropylene.
 439. A process for the formation of linearα-olefins, comprising, contacting, at a temperature of about −100° C. toabout +200° C.: ethylene; a first compound W, which is a neutral Lewisacid capable of abstracting X⁻ to form WX⁻, provided that the anionformed is a weakly coordinating anion, or a cationic Lewis or Bronstedacid whose counterion is a weakly coordinating anion; and a secondcompound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl; R³ and R⁴ are each independently hydrogen, substitutedhydrocarbyl, hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; and Q and S are eachindependently chlorine, bromine, iodine or alkyl; and wherein anα-olefin containing 4 to 40 carbon atoms is produced.
 440. The processas recited in claim 439 wherein said linear α-olefin has the formulaH₂C═CHR¹, wherein R¹ is n-alkyl containing 2 to 30 carbon atoms. 441.The process as recited in claim 439 wherein R² and R⁵ are phenyl. 442.The process as recited in claim 439 wherein R³ and R⁴ are hydrogen,methyl or 1,8-naphthylylene.
 443. The process as recited in claim 440wherein R³ and R⁴ are hydrogen, methyl or 1,8-naphthylylene.
 444. Theprocess as recited in claim 439 wherein said second compound is an alkylaluminum compound.
 445. The process as recited in claim 444 wherein saidalkyl aluminum compound is R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlCl₂, R⁹ ₃Al₂Cl₃, orR⁹AlO, wherein R⁹ is alkyl containing 1 to 25 carbon atoms.
 446. Theprocess as recited in claim 445 wherein R⁹ contains 1 to 4 carbon atoms.447. The process as recited in claim 443 wherein said second compound isR⁹ ₃Al, R⁹ ₂AlCl, R⁹AlCl₂, or R⁹AlO, R⁹ ₃Al₂Cl₃, wherein R⁹ is alkylcontaining 1 to 25 carbon atoms.
 448. The process as recited in claim439 carried out at a temperature of about 25° C. to about 100° C. 449.The process as recited in claim 439 wherein a partial pressure of saidethylene is about atmospheric pressure to about 275 MPa.
 450. Theprocess as recited in claim 439 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring.
 451. A process for the formation oflinear α-olefins, comprising, contacting, at a temperature of about−100° C. to about +200° C.: ethylene and a compound of the formula

wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl; R³ and R⁴ are each independently hydrogen, substitutedhydrocarbyl, hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; T¹ is hydrogen or n-alkylcontaining up to 38 carbon atoms; Z is a neutral Lewis base wherein thedonating atom is nitrogen, sulfur, or oxygen, provided that if thedonating atom is nitrogen then the pKa of the conjugate acid of thatcompound (measured in water) is less than about 6; U is n-alkylcontaining up to 38 carbon atoms; and X is a noncoordinating anion; andwherein an α-olefin containing 4 to 40 carbon atoms is produced.
 452. Aprocess for the production of polyolefins, comprising, contacting, at atemperature of about 0° C. to about +200° C., a compound of the formula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene, wherein: M isNi(II) or Pd(II); A is a π-allyl or π-benzyl group; R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms; and X is a weakly coordinating anion;and provided that; when norbornene or substituted norbornene is present,no other monomer is present; and when M is Pd a diene is not present.453. The process as recited in claim 452 wherein said temperature isabout 20° C. to about 100° C.
 454. The process as recited in claim 452wherein said olefin is ethylene or a linear α-olefin.
 455. The processas recited in claim 452 wherein said olefin is ethylene.
 456. Theprocess as recited in claim 452 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring.
 457. The process as recited in claim 452or 454 wherein a Lewis acid is also present.
 458. The process as recitedin claim 452 wherein M is Ni(II).
 459. The process as recited in claim452 wherein M is PD(II).
 460. The process as recited in claim 452wherein said π-allyl or π-benzyl group is selected from the groupconsisting of

wherein R is hydrocarbyl.
 461. A compound of the formula

wherein: M is Ni(II) or Pd(II); A is a π-allyl or π-benzyl group; R² andR⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; each R¹⁷ is independently hydrocarbyl or substitutedhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms; R¹ is hydrogen, orhydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;and X is a weakly coordinating anion; and provided that when M is Pd adiene is not present.
 462. The compound as recited in claim 461 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a ring.
 463. Thecompound as recited in claim 461 wherein M is Ni(II).
 464. The compoundas recited in claim 461 wherein M is Pd(II).
 465. The compound asrecited in claim 461 wherein said π-allyl or π-benzyl group is selectedfrom the group consisting of

wherein R is hydrocarbyl.
 466. A compound of the formula

wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; R⁵⁴ is hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; eachR⁵⁵ is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, ora functional group; W is alkylene or substituted alkylene containing 2or more carbon atoms; Z is a neutral Lewis base wherein the donatingatom is nitrogen, sulfur, or oxygen, provided that if the donating atomis nitrogen then the pKa of the conjugate acid of that compound(measured in water) is less than about 6, or an olefin of the formulaR¹⁷CH═CHR¹⁷; each R¹⁷ is independently hydrogen, saturated hydrocarbylor substituted saturated hydrocarbyl; and X is a weakly coordinatinganion; and provided that when M is Ni, W is alkylene and each R¹⁷ isindependently hydrogen or saturated hydrocarbyl.
 467. The compound asrecited in claim 466 wherein R³ and R⁴ are each independently hydrogenor hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; and R⁵⁴ is hydrocarbyl.
 468. The compound as recited in claim 466or 467 wherein each R⁵⁵ is independently hydrogen or alkyl containing 1to 10 carbon atoms.
 469. The compound as recited in claim 466 wherein Zis neutral Lewis base.
 470. The compound as recited in claim 469 whereinZ is a dialkyl ether.
 471. The compound as recited in claim 466 whereinZ is R¹⁷CH═CHR¹⁷.
 472. The compound as recited in claim 471 wherein eachR¹⁷ is independently hydrogen or alkyl.
 473. The compound as recited inclaim 471 wherein both of R¹⁷ are hydrogen.
 474. The compound as recitedin claim 466 wherein W is —CH(CH₃)CH₂— or —C(CH₃)₂CH₂—.
 475. Thecompound as recited in claim 471 wherein W is a divalent polymericradical derived from the polymerization of R¹⁷CH═CHR¹⁷.
 476. A processfor the production of a compound of the formula

comprising, heating a compound of the formula

at a temperature of about −30° C. to about +100° for a sufficient timeto produce (XXXVIII), and wherein: R³ and R⁴ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ takentogether are hydrocarbylene or substituted hydrocarbylene to form aring; R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it; each R⁵⁵ is independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or a functional group; R⁵⁶ isalkyl containing 2 to 30 carbon atoms; T⁵ is alkyl; W is alkylenecontaining 2 to 30 carbon atoms; Z is a neutral Lewis base wherein thedonating atom is nitrogen, sulfur, or oxygen, provided that if thedonating atom is nitrogen then the pKa of the conjugate acid of thatcompound (measured in water) is less than about 6; and X is a weaklycoordinating anion.
 477. The process as recited in claim 476 wherein R³and R⁴ are each independently hydrogen or hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a ring; and R⁵⁴ ishydrocarbyl.
 478. The process as recited in claim 476 or 472 whereineach R⁵⁵ is independently hydrogen or alkyl containing 1 to 10 carbonatoms.
 479. The process as recited in claim 476 wherein Z is a dialkylether.
 480. The process as recited in claim 476 wherein W is—CH(CH₃)CH₂—. or —C(CH₃)₂CH₂—
 481. The process as recited in claim 476,477, 479 or 480 wherein T⁵ is methyl.
 482. A process for thepolymerization of olefins, comprising, contacting a compound of theformula

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene, wherein: R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; R⁵⁴ is hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; each R⁵⁵ isindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or afunctional group; W is alkylene or substituted alkylene containing 2 ormore carbon atoms; Z is a neutral Lewis base wherein the donating atomis nitrogen, sulfur, or oxygen, provided that if the donating atom isnitrogen then the pKa of the conjugate acid of that compound (measuredin water) is less than about 6, or an olefin of the formula R¹⁷CH═CHR¹⁷;each R¹⁷ is independently hydrogen, saturated hydrocarbyl or substitutedsaturated hydrocarbyl; and X is a weakly coordinating anion; andprovided that: when M is Ni, W is alkylene and each R¹⁷ is independentlyhydrogen or saturated hydrocarbyl; and when norbornene or substitutednorbornene is present, no other monomer is present.483. The process asrecited in claim 482 wherein R³ and R⁴ are each independently hydrogenor hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; and R⁵⁴ is hydrocarbyl.
 484. The process as recited in claim 482or 483 wherein each R⁵⁵ is independently hydrogen or alkyl containing 1to 10 carbon atoms.
 485. The process as recited in claim 482 wherein Zis a dialkyl ether.
 486. The process as recited in claim 482 wherein Zis R¹⁷CH═CHR¹⁷.
 487. The process as recited in claim 482 wherein eachR¹⁷ is independently saturated hydrocarbyl or hydrogen.
 488. The processas recited in claim 482 wherein both of R¹⁷ are hydrogen.
 489. Theprocess as recited in claim 482 wherein W is —CH(CH₃)CH₂— or—C(CH₃)₂CH₂—.
 490. The process as recited in claim 482 wherein saidtemperature is about 20° C. to about 100° C.
 491. The process as recitedin claim 482 wherein said olefin is ethylene or a linear α-olefin. 492.The process as recited in claim 482 wherein said olefin is ethylene,propylene or a combination of ethylene and propylene.
 493. The processas recited in claim 486 wherein said olefin is ethylene, propylene or acombination of ethylene and propylene.
 494. The process as recited inclaim 489 wherein said olefin is cyclopentene.
 495. The process asrecited in claim 482 wherein said olefin is cyclopentene.
 496. Ahomopolypropylene containing about 10 to about 700 Δ+ methylene groupsper 1000 methylene groups.
 497. The homopolypropylene as recited inclaim 496 containing about 25 to about 300 δ+ methylene groups per 1000methylene groups.
 498. A homopolypropylene wherein a ratio of δ+:γmethylene groups is about 0.5 to about
 7. 499. The homopolypropylene asrecited in claim 498 wherein said ratio is about 0.7 to 2.0.
 500. Ahomopolypropylene in which about 30 to about 85 mole percent of monomerunits are enchained in an ω,1 fashion.
 501. The homopolypropylene asrecited in claim 500 wherein about 30 to about 60 mole percent of themonomer units are enchained in an ω,1 fashion.
 502. A process for theformation of linear α-olefins, comprising, contacting, at a temperatureof about −100° C. to about +200° C.: ethylene; and a Ni[II] of

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; R³ and R⁴ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene or substituted hydrocarbylene to form acarbocyclic ring and wherein an α-olefin containing 4 to 40 carbon atomsis produced.
 503. The process as recited in claim 502 wherein saidlinear α-olefin has the formula H₂C═CHR¹, wherein R¹ is n-alkylcontaining 2 to 30 carbon atoms.
 504. The process as recited in claim502 wherein R² and R⁵ are phenyl.
 505. The process as recited in claim502 wherein R³ and R⁴ are hydrogen, methyl or 1,8-naphthylylene. 506.The process as recited in claim 503 wherein R³ and R⁴ are hydrogen,methyl or 1,8-naphthylylene.
 507. The process as recited in claim 502carried out at a temperature of about 25° C. to about 100° C.
 508. Theprocess as recited in claim 502 wherein a partial pressure of saidethylene is about atmospheric pressure to about 275 MPa.
 509. Theprocess as recited in claim 502 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring.
 510. A polymer blend comprising thepolymer of claim 345, 349, 353, 354, 355, 358, 360 or 361 and one otherpolymer.
 511. A nonwoven fabric wherein at least some fibers comprisethe polymer of claim 345, 349, 353, 354, 355, 358, 360 or
 361. 512. Ashaped part comprising the polymer of claim 345, 349, 353, 354, 355,358, 360 or
 361. 513. A sheet or film comprising the polymer of claim345, 349, 353, 354, 355, 358, 360 or
 361. 514. A nonwoven fabric ormicrofiber comprising the polymer of claim 345, 349, 353, 354, 355, 358,360 or
 361. 515. A laminate wherein one or more of the layers comprisesthe polymer of claim 345, 349, 353, 354, 355, 358, 360 or
 361. 516. Thelaminate as recited in claim 511 wherein a barrier layer is present.517. A fiber comprising the polymer of claim 345, 349, 353, 354, 355,358, 360 or
 361. 518. A foam or foamed object comprising the polymer ofclaim 345, 349, 353, 354, 355, 358, 360 or
 361. 519. A microporousmembrane comprising the polymer of claim 345, 349, 353, 354, 355, 358,360 or
 361. 520. The polymer of claim 345, 349, 353, 354, 355, 358, 360or 361 which is crosslinked.
 521. The polymer of claim 345, 349, 353,354, or 355 which is heat treated.
 522. The polymer as recited in claim521 which has 20 percent or more crystallinity.
 523. A compositioncomprising the polymer of claim 345, 349, 353, 354, 355, 358, 360 or 361and a nucleating agent.
 524. A composition comprising the polymer ofclaim 345, 349, 353, 354, 355, 358, 360 or 361 and a flame ratardant.525. A composition comprising the polymer of claim 345, 349, 353, 354,355, 358, 360 or 361 and an antioxidant.
 526. A composition comprisingthe polymer of claim 345, 349, 353, 354, 355, 358, 360 or 361 and afiller or reinforcer.
 527. A composition comprising the polymer of claim345, 349, 353, 354, 355, 358, 360 or 361 which is electricallyconductive.
 528. A process, comprising, contacting, at a temperature ofabout −80° C. to about +20° C., a compound of the formula(η⁴-1,5-COD)PdMe₂ and a diimine of the formula

to produce a compound of the formula

wherein: COD is 1,5-cyclooctadiene; R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring.
 529. The process asrecited in claim 528 wherein said temperature is about −50° C. to about+10° C.
 530. The process as recited in claim 528 wherein R² and R⁵ areboth 2-t-butylphenyl or 2,5-di-t-butylphenyl, and R³ and R⁴ takentogether are 1,8-naphthylylene, or R³ and R⁴ are both hydrogen ormethyl.
 531. The process as recited in claim 528 wherein R² and R⁵ areeach independently hydrocarbyl, provided that the carbon atom bound tothe imino nitrogen atom has at least two carbon atoms bound to it; andR³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a ring.
 532. The compound asrecited in claim 232, 248, 253, 259, 267, 317, 334, 339, 461 or 466wherein X is part of a heterogeneous support.
 533. The compound asrecited in claim 532 wherein said heterogeneous support ismontmorillonite.
 534. The process as recited in claim 49, 97, 176, 199,280, 299, 451, 452 or 482 wherein X is part of a heterogeneous support.535. The process as recited in claim 49, 97, 176, 199, 280, 299, 451,452 or 482 wherein a polymerization catalyst is supported on aheterogeneous support.
 536. The compound as recited in claim 232, 248,253, 259, 267, 317, 334, 339, 461 or 466 which is supported on aheterogeneous support.
 537. The process as recited in claim 49, 97, 176,199, 280, 299, 451, 452 or 482 wherein the polymerization is run in thegas phase.
 538. The process as recited in claim 478 which is run in afluidized bed reactor.
 539. A flexible pouch made from a single ormultilayer film which comprises the polymer of claim 1, 3, 4, 6, 7, 332or
 343. 540. The polymer of claim 1, 3, 4, 6, 332 or 343 grafted with acompound containing ethylenic unsaturation and a functional group. 541.The polymer as recited in claim 540 wherein said functional group iscarboxyl, carboxylic anhydride, ester or a carboxylate salt.
 542. A wrappackaging film having differential cling, comprising a film laminatehaving at least two layers; an outer reverse layer which comprises apolymer of claim 1, 3, 4, 6, 7, 332 or 343, and a tackifier present insufficent amount to impart cling properties; and an outer obverse layerwhich has a density of at least about 0.916 g/mL and which has little orno cling; and provided that a density of said outer reverse layer is atleast 0.008 g/mL less than that of a density of said outer obverselayer.
 543. A fine denier fiber comprising the polymer of claim 1, 3, 4,6, 7, 332 or
 343. 544. A composition, comprising, a polymer of claim 1,3, 4, 6, 7, 332 or 343 and an antifogging agent.
 545. The process asrecited in claim 13, 15 or 142 wherein said bidentate ligand or secondcompound is (XXX) and n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, andboth of R⁴⁴ and R⁴⁵ are 9-anthracenyl.
 546. The process as recited inclaim 65 or 84 wherein said compound or said second compound is (XVII)and n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, and both of R⁴⁴ andR⁴⁵ are 9-anthracenyl.
 547. The process as recited in claim 65 or 84wherein said compound or said second compound is (XVII) and n is 2, allof R³⁰, R²⁸ and R²⁹ are hydrogen, both of R⁴⁴ and R⁴⁵ are 9-anthracenyl,M is Ni, and n is
 2. 548. The compound or process as recited in claim299 or 317 wherein M is Ni or Pd and m is
 2. 549. The process as recitedin claim 299 wherein M is Ni.
 550. The process as recited in claim 49wherein said olefin comprises cyclopentene.
 551. The process as recitedin claim 65 wherein said olefin comprises cyclopentene.
 552. The processas recited in claim 452 wherein said olefin comprises cyclopentene. 553.The process as recited in claim 548 wherein said monomer comprisescyclopentene.
 554. The process as recited in claim 17, 48, 124, 151,156, 167, 180, 231, 298, 316, 550, 551, 552 or 553 wherein cyclopenteneis a solvent.
 555. The process as recited in claim 37 wherein: R² and R⁵are both 2,4,6-trimethylphenyl or 2,6-dimethylphenyl; R³ and R⁴ takentogether are 1,8-naphthylylene; y and z are both 1; M is Ni; Q and S areboth chloride, iodide or bromide; and m is
 2. 556. The process asrecited in claim 555 wherein said first compound is an alkylaluminumcompound.
 557. The process as recited in claim 556 wherein saidalkylaluminum compound is ethylaluminum dichloride or methylaluminoxane.558. The process as recited in claim 555, 556 or 557 wherein saidmonomer comprises cyclopentene.
 559. The process as recited in claim 558wherein cyclopentene is a solvent.
 560. The polymer as recited in claim1, 3, 4, 6, 332 or 343 which has: a melt flow ratio, I10/I2≧5.63; amolecular weight distribution, Mw/Mn, defined by the equation:Mw/Mn≦(I10/I2)−4.63; and a critical shear rate at onset of surface meltfracture of at least 50 percent greater than the critical shear rate atthe onset of surface melt fracture of a linear olefin polymer havingabout the same I2 and Mw/Mn.
 561. A composition comprising: the polymeras recited in claim 1, 3, 4, 6, 332 or 343 which has: a melt flow ratio,I10/I2, > or =5.63; a molecular weight distribution, Mw/Mn, defined bythe equation: Mw/Mn<OR=(I10/I2)−4.63; and a critical shear rate at onsetof surface melt fracture of at least 50 percent greater than thecritical shear rate at the onset of surface melt fracture of a linearolefin polymer having about the same I2 and Mw/Mn; and at least oneother: natural polymer; a synthetic polymer chosen from the polymer ofclaims 1, 3, 4, 6, 332, or 343; or a conventional high densitypolyethylene, low density polyethylene or linear low densitypolyethylene polymer.
 562. The polymer as recited in claim 1, 3, 4, 6,332, 343, 383, 384, 385, 386 or 387 which has a melt flow ratio,I10/I2≧5.63, a molecular weight distribution, Mw/Mn, defined by theequation: Mw/Mn≦(I10/I2)−4.63, and a critical shear stress at onset ofgross melt fracture of greater than about 400 kPa.